KR102555333B1 - Photosensitive composition for color filter and color filter - Google Patents

Abstract

[Problem] The present invention provides a resist pattern having good viscosity stability of a photosensitive coloring composition, good patterning characteristics (resolution, linearity, dimensional stability, development stability) when forming a film, and good dimensional stability and linearity. It is an object of the present invention to provide a photosensitive coloring composition capable of forming, and a color filter. [Solution] In the presence of a reaction product of a hydroxyl group of compound (a) having two hydroxyl groups and one thiol group in the molecule and an acid anhydride group of pyromellitic anhydride and/or trimellitic anhydride, ethylenically unsaturated hydroxyl group-containing A resin obtained by reacting a hydroxyl group of a hydroxyl group-containing polymer obtained by polymerizing an ethylenically unsaturated monomer (c) containing a monomer (b), and an isocyanate group of a compound (d) having one isocyanate group and at least one (meth)acryloyl group And, the content of the hydroxyl group-containing ethylenically unsaturated monomer (b) is 35% by mass or more and 80% by mass or less with respect to the total amount of the ethylenically unsaturated monomer (c). The photosensitive coloring composition for color filters containing a resin type dispersant.

Description

Photosensitive composition for color filters, and color filters {PHOTOSENSITIVE COMPOSITION FOR COLOR FILTER AND COLOR FILTER}

This invention relates to the photosensitive coloring composition which can be used for formation of the color filter used for a liquid crystal display device or an organic electroluminescent display.

A color filter is formed by arranging two or more fine strip-shaped filter segments of different colors parallel to each other (in a stripe shape) or crossing each other on a transparent substrate such as a glass substrate, or by arranging two or more fine filter segments of different colors. It is made by arranging the filter segments to be sequentially arranged in each of the longitudinal and transverse directions. The filter segments have a small dimension of several microns to several 100 microns, and are arranged orderly in a predetermined arrangement for each color.

Currently, as a method for producing a color filter, a method called a pigment dispersion method using a pigment excellent in various resistances such as light resistance and heat resistance as a coloring material is becoming mainstream. Moreover, in the pigment dispersion method, a color filter is manufactured by the following method. First, a photosensitive coloring composition (pigment resist) obtained by dispersing a pigment in a photosensitive transparent resin solution is applied to a transparent substrate such as glass. After removing the solvent from this coating film by drying, this coating film is exposed in a pattern corresponding to a filter segment of a certain color. Next, the unexposed portion of the coating film is removed by development, and then a treatment such as heating is performed as necessary. In this way, a filter segment pattern of one color tone is obtained. Then, by performing the same operation as this, filter segment patterns of different colors are formed to complete the color filter.

Recently, high color reproduction of displays has become an important trend. High color reproducibility of the display is centered on the study of improving the color reproducibility of the backlight, but it is necessary to use a very dark color to improve the color reproducibility also for the color filter. In such a case, in the exposure step of forming a pattern of the color filter, since the amount of light reaching the bottom of the coating film is weak, photocuring is likely to be insufficient, and a problem that a pattern of a desired shape cannot be obtained occurs.

Specifically, when the size of the pattern obtained in the color filter manufacturing process shifts the exposure amount in the exposure process, the dimensional stability within a certain extent can be obtained with the photosensitive coloring composition, but it is difficult to achieve high color reproduction. In photosensitive coloring compositions, such dimensional stability tends to deteriorate. Similarly, in the photosensitive coloring composition that achieves high color reproduction, the linearity of the pattern tends to deteriorate.

Here, Patent Document 1 discloses a composition using a polymer having a specific structure. Patent Document 2 discloses a method of providing an anchor layer on a substrate. In Patent Document 3, a composition using a polymer having a specific structure is disclosed. Patent Document 4 discloses a composition using a polymerization initiator having a specific structure. Patent Document 5 discloses a composition using a thiol-based compound.

Patent Document 1: Japanese Unexamined Patent Publication No. 2013-254047 Patent Document 2: Japanese Unexamined Patent Publication No. 2013-073115 Patent Document 3: Japanese Unexamined Patent Publication No. 2012-108227 Patent Document 4: Japanese Unexamined Patent Publication No. 2011-002796 Patent Document 5: Japanese Unexamined Patent Publication No. 2010-039475

However, in the conventional composition, there was a problem that all of the pattern shape after development, dimensional stability, and linearity of the pattern could not be improved.

The present invention provides a resist pattern having good viscosity stability of a photosensitive coloring composition, good patterning characteristics (resolution, linearity, dimensional stability, developing stability) when forming a film, and good dimensional stability and linearity. It is an object of the present invention to provide a photosensitive coloring composition that can be used, and a color filter.

The photosensitive coloring composition for color filters of the present invention,

<1> contains a colorant (A), a resinous dispersant (B), a photopolymerization initiator (C), an organic solvent (D) and a polymerizable compound (E);

In the presence of a reaction product between the hydroxyl group of the compound (a) having two hydroxyl groups and one thiol group in the molecule of the resinous dispersant (B) and an acid anhydride group of pyromellitic anhydride and/or trimellitic acid anhydride, the hydroxyl group Isocyanate of compound (d) having a hydroxyl group of a hydroxyl group-containing polymer obtained by polymerizing an ethylenically unsaturated monomer (c) containing an ethylenically unsaturated monomer (b), one isocyanate group, and one or more (meth)acryloyl groups It is a resin in which a group has been reacted, and the content of the structural unit derived from the hydroxyl group-containing ethylenically unsaturated monomer (b) is 35% by mass or more and 80% by mass or less with respect to the total amount of the structural unit derived from the ethylenically unsaturated monomer (c). A photosensitive coloring composition for filters.

<2> ((c) total mass of structural units derived from ethylenically unsaturated monomers + (d) total mass of structural units derived from a compound having one isocyanate group and one or more (meth)acryloyl groups)/ ((d) Number of moles of (meth)acryloyl groups contained in structural units derived from compounds having one isocyanate group and one or more (meth)acryloyl groups) In the side chain of the resin type dispersant (B) The photosensitive coloring composition for a color filter wherein the double bond equivalent (Z) of is 300 to 600 g/mol.

<3> The content of the structural unit derived from the ethylenically unsaturated monomer (b) containing a hydroxyl group in the resinous dispersant (B) is 38% by mass or more 60 with respect to the total amount of the structural unit derived from the ethylenically unsaturated monomer (c) The photosensitive coloring composition for said color filter which is mass % or less.

<4> The said photosensitive coloring composition for color filters whose content of a coloring agent (A) is 40 mass % or more with respect to the total amount of non-volatile matter of the photosensitive coloring composition for color filters.

<5> The said photosensitive coloring composition for color filters in which a photoinitiator (C) contains an oxime ester type compound.

<6> The color filter provided with the filter segment formed from the said photosensitive coloring composition for color filters on a base material.

By using the resin type dispersant of the specific structure of the present invention, while satisfying the various patterning properties (resolution, linearity, dimensional stability, development stability) required for the photosensitive coloring composition, the viscosity stability as a photosensitive coloring composition, dimensional stability, A photosensitive coloring composition for color filters having excellent linearity can be provided. In addition, a high-quality color filter using the photosensitive coloring composition for color filters can be provided.

EMBODIMENT OF THE INVENTION Below, embodiment of this invention is described in detail. Also, in the present specification, (meth)acrylate means acrylate and/or methacrylate, and (meth)acrylic acid means acrylic acid and/or methacrylic acid.

<Photosensitive coloring composition for color filters>

The photosensitive coloring composition for color filters of the present invention contains a coloring agent (A), a resin type dispersant (B), a photopolymerization initiator (C), an organic solvent (D) and a polymerizable compound (E), and a resin type dispersant (B). ) is an ethylenically unsaturated monomer containing a hydroxyl group in the presence of a reaction product of a hydroxyl group of compound (a) having two hydroxyl groups and one thiol group in the molecule and an acid anhydride group of pyromellitic anhydride and/or trimellitic anhydride. It is a resin obtained by reacting the hydroxyl group of a hydroxyl group-containing polymer obtained by polymerizing the ethylenically unsaturated monomer (c) containing (b) with the isocyanate group of the compound (d) having one isocyanate group and one or more (meth)acryloyl groups. , It is characterized in that the content of the hydroxyl group-containing ethylenically unsaturated monomer (b) is 35% by mass or more and 80% by mass or less with respect to the total amount of the ethylenically unsaturated monomer (c).

Hereinafter, the photosensitive coloring composition for color filters of the present invention will be described in detail.

<Resin type dispersing agent (B)>

The resin type dispersant (B) of the present invention is a reaction product of the hydroxyl group of the compound (a) having two hydroxyl groups and one thiol group and the acid anhydride group of pyromellitic anhydride and/or trimellitic anhydride. Step 1, subsequently, by radically polymerizing the ethylenically unsaturated monomer (c) containing the ethylenically unsaturated monomer (b) containing a hydroxyl group using the thiol group remaining in the reaction product as a chain transfer agent, thereby obtaining a vinyl polymer portion having a hydroxyl group It is obtained by passing through the second step of producing the introduced hydroxyl group-containing polymer and the third step of reaction of the compound (d) having one isocyanate group and one or more (meth)acryloyl groups. A plurality of carboxy group moieties in the resin type dispersant (B) of the present invention function as a pigment adsorption portion, and a vinyl polymer portion functions as a solvent affinity portion.

In addition, the resin type dispersant (B) of the present invention has a complex structure obtained through a plurality of reactions of a reaction between a hydroxyl group and an acid anhydride group, a radical polymerization reaction using a residual thiol group as a chain transfer agent, and a reaction between a residual hydroxyl group and an isocyanate group. Since it is impossible to represent with a general formula (structure) or is not realistic at all, the manufacturing method is described.

(Compound (a) having two hydroxyl groups and one thiol group in the molecule)

The compound (a) having two hydroxyl groups and one thiol group in the molecule is, for example, 1-mercapto-1,1-methane diol, 1-mercapto-1,1-ethanediol, 3-mercapto- 1,2-propanediol (alias: 1-thioglycerol), 2-mercapto-1,3-propanediol, 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1, 3-propanediol, 2-mercapto-2-ethyl-1, 3-propanediol, 1-mercapto-2, 2-propanediol, 2-mercaptoethyl-2-methyl-1, 3-propanediol, 2-mercaptoethyl-2-ethyl-1, 3-propanediol, etc. are mentioned.

In the present specification, the vinyl polymer portion formed by radical polymerization of an ethylenically unsaturated monomer (c) containing a hydroxyl group-containing ethylenically unsaturated monomer (b) is a compound having two hydroxyl groups and one thiol group in the structure of the resin type dispersant B It is a continuous part that does not include a polyester part having a carboxy group obtained by reacting (a) with pyromellitic anhydride and/or trimellitic acid anhydride. In one molecule constituting the resin type dispersant (B), when only trimellitic anhydride is used, one vinyl polymer moiety and when pyromellitic anhydride is used, a plurality of vinyl polymer moieties are contained. It is more preferable to use pyromellitic anhydride from a viewpoint of dispersion stability.

A known catalyst can be used as a catalyst used when reacting the acid anhydride group and hydroxyl group of the present invention. For example, triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabi Cyclo-[4.3.0]-5-nonene, monobutyltin oxide, etc. are mentioned.

Acid anhydride in pyromellitic anhydride in the reaction product of the hydroxyl group of compound (a) having two hydroxyl groups and one thiol group obtained in the first step and the acid anhydride group of pyromellitic anhydride and/or trimellitic anhydride. The number of moles of groups is (p), the number of moles of acid anhydride groups in trimellitic acid anhydride is (t), and the number of moles of hydroxyl groups in compound (a) having two hydroxyl groups and one thiol group in the molecule is (o). In this case, the molar ratio is preferably 0.3<[(p)+(t)]/(o)<1.0, more preferably 0.5<[(p)+(t)]/(o)<1.0 , most preferably 0.6<[(p)+(t)]/(o)<0.8. If it is 0.3 or less, the acid anhydride residue that is the pigment adsorption portion may decrease, and the acid value of the resin may also decrease in some cases. If it is 1.0 or more, unreacted acid anhydride groups may remain and storage stability may deteriorate.

Next, the hydroxyl group of the compound (a) having two hydroxyl groups and one thiol group and the thiol group remaining in the reaction product of the acid anhydride group of pyromellitic anhydride and/or trimellitic anhydride is used as a chain transfer agent to form a hydroxyl group. The 2nd process of manufacturing the hydroxyl group-containing polymer into which the hydroxyl group-containing ethylenically unsaturated monomer was introduce|transduced by radically polymerizing the ethylenically unsaturated monomer (c) containing containing ethylenically unsaturated monomer (b) is demonstrated. By copolymerizing the ethylenically unsaturated monomer (b) containing a hydroxyl group in the second step, a hydroxyl group can be introduced into the vinyl polymer portion of the dispersant, and in the third step one isocyanate group and one or more (meth)acryloyl groups are formed. Branches can be reacted with compound (d).

(hydroxyl group-containing ethylenically unsaturated monomer (b))

As the hydroxyl group-containing ethylenically unsaturated monomer (b), any monomer may be used as long as it has a hydroxyl group and has an ethylenically unsaturated double bond. Specifically, a (meth)acrylate-based monomer having a hydroxyl group, for example, 2 -hydroxyethyl (meth)acrylate, 2 (or 3)-hydroxypropyl (meth)acrylate, 2 (or 3 or 4)-hydroxybutyl (meth)acrylate and cyclohexanedimethanol mono (meth) Hydroxyalkyl (meth)acrylates such as acrylate, and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate, or (meth)acrylamide-based monomers having a hydroxyl group, for example , N-(2-hydroxyethyl) (meth)acrylamide, N-(2-hydroxypropyl) (meth)acrylamide, N-(2-hydroxybutyl) (meth)acrylamide, etc. Hydroxyalkyl) (meth)acrylamide, or a vinyl ether monomer having a hydroxyl group, such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, 2- (or 3 - or 4-) hydroxyalkyl vinyl ethers such as hydroxybutyl vinyl ether, or allyl ether monomers having a hydroxyl group, such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ethers, hydroxyalkyl aryl ethers such as 2-(or 3- or 4-) hydroxybutyl allyl ether.

In addition, the above hydroxyalkyl (meth) acrylate, alkyl-α-hydroxyalkyl acrylate, N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl vinyl ether or hydroxyalkyl allyl ether with alkylene An ethylenically unsaturated monomer obtained by adding an oxide and/or lactone can also be used as the hydroxyl group-containing ethylenically unsaturated monomer (b) in the method of the present invention. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and a combination of two or more of these are used. When two or more types of alkylene oxides are used in combination, any one of random and/or block may be sufficient as the bonding form. As the lactone added, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group of 1 to 6 carbon atoms, and a combination of two or more of these are used. What added both alkylene oxide and lactone may be sufficient.

(other ethylenically unsaturated monomers)

Ethylenically unsaturated monomers other than the hydroxyl group-containing ethylenically unsaturated monomer (b) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acryl rate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2, 2, Alkyl (meth)acrylates such as 4-trimethylcyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, and isobornyl (meth)acrylate;

aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate;

Heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate; Alkoxy polyalkylene glycol (meth)acrylates such as methoxypolypropylene glycol (meth)acrylate and ethoxypolyethylene glycol (meth)acrylate Acrylates;

(meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, acryloylmol (N-substituted) (meth)acrylamides such as porin;

amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate;

Nitriles, such as (meth)acrylonitrile, are mentioned.

In addition, as monomers that can be used in combination with the acrylic monomer, styrenes such as styrene, α-methylstyrene, indene, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether Fatty-acid vinyls, such as vinyl ethers, such as these, vinyl acetate, and vinyl propionate, are mentioned.

In addition, a carboxy group-containing ethylenically unsaturated monomer may be used in combination. As the carboxyl group-containing ethylenically unsaturated monomer, one or two or more types can be selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like.

The content of the hydroxyl group-containing ethylenically unsaturated monomer (b) is 35% by mass or more and 80% by mass or less, preferably 38% by mass or more and 60% by mass or less, more preferably is 40% by mass or more and 50% by mass or less.

In the resin type dispersant of the present invention, the carboxyl group-containing ethylenically unsaturated monomer is most preferably acrylic acid or methacrylic acid, and the carboxy group in the ethylenically unsaturated monomer (c) including the hydroxyl group-containing ethylenically unsaturated monomer (b) It is preferable to use 2.5-10.0 mass % of content of containing ethylenically unsaturated monomer, More preferably, it is 2.5-5.0 mass %. When it is less than 2.5% by mass, patterning aptitude such as linearity and dimensional stability at the time of color filter production deteriorates, and when it exceeds 10.0% by mass, pigment dispersion stability sometimes deteriorates.

Next, the 3rd process which makes the said hydroxyl-containing compound and the compound (d) which has one isocyanate group and one or more (meth)acryloyl groups react is demonstrated. The dispersing agent of this invention is obtained by making the hydroxyl group of this hydroxyl-containing compound react with the isocyanate group of the compound (d) which has one isocyanate group and one or more (meth)acryloyl groups. As a result, a curable dispersant can be obtained which can optionally introduce a (meth)acryloyl group into mainly a vinyl polymer portion in the dispersant and has curability at a solvent-affinity portion.

(Compound (d) having one isocyanate group and one or more (meth)acryloyl groups)

As the compound (d) having one isocyanate group and one or more (meth)acryloyl groups used in the third step, a compound having one isocyanate group and one or two (meth)acryloyl groups is preferable. As such, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate are preferable.

The compound (d) having one isocyanate group and one or more (meth)acryloyl groups used in the present invention is not limited to the compounds exemplified above, and has any structure as long as it has an isocyanate group and one or more (meth)acryloyl groups. It doesn't matter if you are doing These may be used alone or in combination.

The molar ratio of the hydroxyl group in the hydroxyl group-containing compound and the isocyanate group in the compound (d) having one isocyanate group and one or more (meth)acryloyl groups is 1 isocyanate group and 1 mole of the hydroxyl group in the hydroxyl group-containing compound. It is preferable that the isocyanate group in the compound (d) having two or more (meth)acryloyl groups is 0.2 to 1.0 moles, more preferably 0.5 to 1.0 moles, and most preferably 0.8 to 1.0 moles. If it is less than 0.2 mol, the amount of (meth)acryloyl groups will decrease, so curability may be insufficient, and if it exceeds 1.0 mol, unreacted isocyanate groups remain in the resin, and storage stability may deteriorate. . The reaction temperature is carried out in the range of 50°C to 150°C, preferably 70°C to 120°C. When the reaction temperature is less than 50°C, the reaction rate is slow, and when the reaction temperature exceeds 150°C, the urethane group generated by the reaction decomposes.

The number of moles of (meth)acryloyl groups introduced into the resin type dispersant (B) obtained by reaction of a compound having a hydroxyl group in the hydroxyl group-containing compound with one isocyanate group and one or more (meth)acryloyl groups is certain. It is preferable that it is positive. Generally, the amount of double bonds in a resin is calculated as (total weight of the resin)/(number of moles of double bonds contained in the weight of the resin), and the double bond equivalent (g/mol) is expressed as a numerical value. However, in the present invention, it is not the double bond equivalent of the entire resin, ((c) total mass of ethylenically unsaturated monomers + (d) total mass of compounds having one isocyanate group and one or more (meth)acryloyl groups) / Double bond equivalent in the side chain of the resin type dispersant (B) represented as ((d) the number of moles of the (meth)acryloyl group contained in the compound having one isocyanate group and one or more (meth)acryloyl groups) ( Z) affects the linearity and dimensional stability at the time of color filter creation. In the present invention, it is preferable that the value of Z is 300 to 600 g/mol because of linearity and dimensional stability at the time of color filter creation.

The weight average molecular weight of the obtained dispersion of the present invention is preferably 2,000 to 10,000, more preferably 5,000 to 30,000. When the weight average molecular weight is less than 2,000, the stability of the pigment composition may decrease, and when it exceeds 100,000, the interaction between resins becomes stronger and the pigment composition may thicken.

The acid value of the resin type dispersant of the present invention is preferably 5 to 200 mgKOH/g, more preferably 5 to 150 mgKOH/g, and particularly preferably 5 to 100 mgKOH/g. If the acid value is less than 5 mgKOH/g, the pigment adsorption ability may decrease and a problem may occur in the pigment dispersibility, and if it exceeds 200 mgKOH/g, the interaction between the resins becomes strong and the viscosity of the pigment dispersion composition may increase.

<colorant (A)>

The photosensitive coloring composition for color filters of this invention may also contain a pigment or dye as a coloring agent. As a pigment, an organic or inorganic pigment can be used individually or in mixture of 2 or more types. The pigment is preferably a pigment having high color development and high heat resistance, particularly a pigment having high thermal decomposition resistance, and an organic pigment is usually used. Below, the specific example of the organic pigment usable for the coloring composition for color filters is shown by a color index number.

＜Organic pigments＞

The red pigment is, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37 , 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53 :1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81 :1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144 ; 200 ,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247, 249 ,250,251,253,254,255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275, 276 , 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, the diketopyrrolopyrrole pigment described in Japanese Patent Publication No. 2011-523433, or Japanese Patent Publication 2014-112527 An azo pigment, the azo pigment of Unexamined-Japanese-Patent No. 2013-161026, etc. are mentioned. Among these, from the viewpoint of heat resistance, light resistance and transmittance of the filter segment, C.I. Pigment Red 48:1, 122, 177, 224, 242, 254 are preferred, and C.I. Pigment Red 177, 254 are more preferred.

In the red coloring composition, an orange pigment such as C.I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71 or 73 and/or a yellow pigment described later may be used in combination.

The blue pigment is, for example, C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 are preferred, and more preferably C.I.Pigment Blue 15:1. C.I. Pigment Blue 15:6. Moreover, it is also preferable to use an aluminum phthalocyanine pigment, and the aluminum phthalocyanine pigment etc. which are described in Unexamined-Japanese-Patent No. 2004-333817, Unexamined-Japanese-Patent No. 4893859, etc. can also be used.

Moreover, you may use together the purple pigment mentioned later in a blue coloring composition.

The purple pigment is, for example, C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 etc. are mentioned. Among these, C.I. Pigment Violet 19 or 23 is preferable, and C.I. Pigment Violet 23 is more preferable from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment.

The green pigment is, for example, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 62, 63, zinc phthalocyanine pigments described in Japanese Patent Laid-Open No. 2008-19383, Japanese Patent Laid-Open No. 2007-320986, Japanese Patent Laid-Open No. 2004-70342, etc., Japanese Patent No. 4893859, etc. An aluminum phthalocyanine pigment etc. are mentioned. Among these, from a viewpoint of transmittance, C.I. Pigment Green 36 or 58 is preferable.

In addition, a yellow pigment described later may be used in combination with the green coloring composition.

In yellow pigments, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35 :1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95 1 47 ,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180, 181 , 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, and the quinophthalone compounds described in Japanese Unexamined Patent Publication No. 2012226110, etc., but are not particularly limited thereto. . Among these, from the viewpoint of heat resistance, light resistance and transmittance of the filter segment, as the yellow pigment, at least one selected from C.I. Pigment Yellow 138, 139, 150, 185 and quinophthalone pigments described in Japanese Patent Laid-Open No. 2012-226110 It is preferable to be a species. More preferably, they are C.I. Pigment Yellow 139, 150, and 185.

Examples of the quinophthalone-based pigment described in Japanese Unexamined Patent Publication No. 2012-226110 include compounds shown below.

[Tue 1]

[Tue 2]

[Tue 3]

In the cyan coloring composition for forming the cyan filter segment, for example, C.I. Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81, etc., alone Or you can use a mixture.

In the magenta coloring composition for forming the magenta color filter segment, for example, C.I. Pigment Violet 1, 19, C.I. Pigment Red 144, 146, 177, 169, 81, etc., a purple pigment and a red pigment may be used alone or in combination. can A yellow pigment may be used in combination with the magenta color composition.

In addition, as inorganic pigments, titanium oxide, barium sulfate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron (III) oxide, cadmium red, ultramarine blue, royal blue, chromium oxide green, cobalt green, umber (UMBER ), synthetic iron black, and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good applicability, sensitivity, developability, etc. while balancing chroma and brightness.

(Pigment Refinement)

The organic pigment is preferably refined by salt milling or the like in order to achieve high transmittance and high contrast. The primary particle size of the pigment is preferably 10 nm or more because of its good dispersion in the colorant carrier. Also, since a filter segment with high contrast can be formed, it is preferably 80 nm or less. A particularly preferable range is the range of 20 to 60 nm.

When salt milling a pigment, you may add resin as needed. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is preferably solid at room temperature and insoluble in water, more preferably partially soluble in the organic solvent. The amount of resin used is preferably in the range of 5 to 200% by mass based on the total weight of the pigment (100% by mass).

<dye>

In the coloring composition according to the embodiment of the present invention, a dye may be used as a coloring agent. As the dye, any of acid dyes, direct dyes, basic dyes, form dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes and the like can be used. In addition, they may be in the form of a derivative of these or a lake pigment obtained by forming a dye into a lake.

In addition, in the case of an acidic dye having an acidic group such as sulfonic acid or carboxylic acid, or a direct dye, an inorganic salt of an acid dye, a quaternary ammonium salt compound with an acid dye, a tertiary amine compound, a secondary amine compound, or a first By using a salt-formation compound with a nitrogen-containing compound such as a quaternary amine compound, or a resin component having such a functional group and using it as a salt-former compound by using it as a salt-former compound, or by sulfonamidation and using it as a sulfonic acid amide compound, resistance is excellent. , it is preferable because it can be used as a coloring composition with excellent fastness.

A salt-formation compound of an acid dye and a compound having an onium salt group is also preferred because of its excellent fastness. More preferably, the compound having an onium salt group is a resin having a cationic group in its side chain.

In the case of the form of a basic dye, it can be used by forming a salt using an organic acid, perchloric acid, or a metal salt thereof. Salt-formation compounds of basic dyes are preferable because of their excellent resistance and compatibility with pigments, and are organic sulfonic acids and organic sulfuric acids, fluorine group-containing phosphorus anion compounds and fluorine group-containing counter components that act as counter ions with basic dyes. It is more preferable to use a boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugated base of an organic acid having a halogenated hydrocarbon group, or a salt-formation compound obtained by forming a salt with an acidic dye.

Moreover, when it has a polymerizable unsaturated group in the dye backbone, it is preferable because it can be set as a dye with excellent resistance.

Moreover, when a dye has an oxetane group, the coloring composition containing the said dye is excellent in heat resistance after hardening. The dye having an oxetane group can be achieved by, for example, using an ethylenically unsaturated monomer containing an oxetane structure for a resin constituting a salt-formation compound containing the dye.

In one embodiment, the chemical structure of the dye is, for example, azo-based dyes, azomethine-based dyes (indoaniline-based dyes, indophenol-based dyes, etc.), dipyrromethene-based dyes, quinone-based dyes (benzoquinone-based dyes, naphthoquinone-based dyes, anthraquinone-based dyes, anthrapyridone-based dyes, etc.), carbonium-based dyes (diphenylmethane-based dyes, triphenylmethane-based dyes, xanthene-based dyes, acridine-based dyes, etc.), quinoneimine-based dyes (jade Photographic dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes etc.), quinophthalone-based dyes, phthalocyanine-based dyes, subphthalocyanine-based dyes, perinone-based dyes, indigo-based dyes, thioindigo-based dyes, quinoline-based dyes, nitro-based dyes, nitroso-based dyes, and such metal complex dyes, etc. and dye structures derived from dyes selected from

Among these dye structures, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and suku are selected from the viewpoint of color characteristics such as color, color separability, and color unevenness. A dye structure derived from a dye selected from arylium-based dyes, quinophthalone-based dyes, phthalocyanine-based dyes, and subphthalocyanine-based dyes is preferred, and xanthene-based dyes, cyanine-based dyes, triphenylmethane-based dyes, anthraquinone-based dyes, A dye structure derived from a dye selected from dipyrromethene-based dyes and phthalocyanine-based dyes is more preferable. For specific dye compounds capable of forming a dye structure, see "New Edition Dye Handbook" (Edited by Synthetic Organic Chemistry Association; Maruzen, 1970), "Color Index" (The Society of Dyers and Colorists), "Dye Handbook" (Okawara et al. Edition; KODANSHA, 1986) and the like.

Examples of dyes in another embodiment include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, methine dyes, diaryl methane dyes, and triaryl methane dyes. Dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes, naphthoquinone dyes, oxazine dyes, perylene dyes, diketopyrrolopyrrole dyes, quinacridone dyes , anthanthrone dyes, iso-indolinone dyes, isoindoline dyes, indanthrone dyes, coumarin dyes, quinacridone dyes, pyrancerone dyes, flavanthrone dyes, perinone dyes, etc. but is not limited to these.

Examples of organic dyes that can be used in another embodiment include triarylmethane-based dyes, xanthene-based dyes, and anthraquinone-based dyes, and among them, it is preferable to use a xanthene-based dye.

[Xanthene dye]

The xanthene-based dye that can be preferably used is one that exhibits red or purple colors, and preferably has any form of an oil-soluble dye, an acid dye, a direct dye, or a basic dye. Further, it may be in the form of a lake pigment obtained by forming a lake of such a dye.

Among these, it is preferable to use a xanthene-based oil-soluble dye or a xanthene-based acid dye because of its excellent color.

Examples of red and purple colors include oil-soluble dyes such as C.I.Solvent Red and C.I.Solvent Violet, basic dyes such as C.I.BASIC Red and C.I.BASIC Violet, acidic dyes such as C.I.Acid Red and C.I.Acid Violet, C.I.Direct Red and C.I.Direct Those belonging to direct dyes, such as Violet, etc. are mentioned.

Here, the direct dye has a sulfonic acid group (-SO ₃ H, -SO ₃ Na) in its structure, and for this disclosure, the direct dye is regarded as an acid dye.

[Salting of xanthene-based dyes, sulfonamidation]

In addition, it is preferable to use a xanthene-type basic dye after it is salted using an organic acid or perchloric acid. As the organic acid, it is preferable to use an organic sulfonic acid or an organic carboxylic acid. Among them, it is preferable to use naphthalenesulfonic acids such as Tobias acid and perchloric acid from the viewpoint of resistance.

In addition, the xanthene acid dye is a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, or the like, or a resin component having such a functional group and used as a salt-formation compound, or sulfone It is preferable from the viewpoint of resistance to amidate and use as a sulfonic acid amide compound.

Salt-formation compounds of xanthene-based acid dyes and/or sulfonic acid amide compounds of xanthene-based acid dyes are preferable because of their excellent color and resistance, and quaternary ammonium salt compounds, which are counter components acting as counter ions, are preferred for xanthene-based acid dyes. It is more preferable to use a sulfonic acid amide compound obtained by sulfonamidating a compound obtained by forming a salt using the acid dye and a xanthene-based acid dye.

Moreover, among xanthene pigments, rhodamine pigments are preferable because they are excellent in color development and resistance.

Hereinafter, the form of the xanthene-based dye will be described in detail.

[xanthene oil-soluble dye]

As the xanthene-based oil-soluble dyes, C.I. Solvent Red 35, C.I. Solvent Red 36, C.I. Solvent Red 42, C.I. Solvent Red 43, C.I. Solvent Red 44, C.I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48 , C.I.Solvent Red 49, C.I.Solvent Red 72, C.I.Solvent Red 73, C.I.Solvent Red 109, C.I.Solvent Red 140, C.I.Solvent Red 141, C.I.Solvent Red 237, C.I.Solvent Red 246, C.I.Solvent Violet 2, C.I.Sol vent Violet 10 etc. can be mentioned.

Among them, C.I. Solvent Red 35, C.I. Solvent Red 36, C.I. Solvent Red 49, C.I. Solvent Red 109, C.I. Solvent Red 237, C.I. Solvent Red 246 and C.I. Solvent Violet 2, which are rhodamine-based oil-soluble dyes with high color development, are more preferable.

[Xanthene basic dye]

Examples of xanthene-based basic dyes include C.I.BASIC Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), and C.I.BASIC Violet 10 (Rhodamine B). Among them, it is preferable to use C.I.BASIC Red 1 and C.I.BASIC Violet 10 from the viewpoint of excellent color development.

[Xanthene acid dye]

As the xanthene acid dye, C.I.Acid Red 51 (erythrosine (food red No. 3)), C.I. Acid Red 52 (acid rhodamine), C.I. Acid Red 87 (eosin G (food red No. 103)), C.I. Acid Red 92 (Acid Phloxine PB (Food Red No. 104)), C.I. Acid Red 289, C.I. Acid Red 388, Rose Bengal B (Food Red No. 5), Acid Rhodamine G, and C.I. Acid Violet 9 are preferably used.

Among them, in terms of heat resistance and light resistance, C.I.Acid Red 87, C.I.Acid Red 92, and C.I.Acid Red 388, which are xanthene-based acid dyes, or C.I.Acid Red 52 (acid rhodamine), C.I.Acid Red, which are rhodamine-based acid dyes 289, Acid Rhodamine G, C.I. Acid Violet 9 is more preferably used.

Among these, it is most preferable to use C.I. Acid Red 52 and C.I. Acid Red 289, which are rhodamine-based acid dyes, in view of their excellent color development, heat resistance and light resistance.

The acid dye (not limited to xanthene type) is preferably a salt-formation compound of an acid dye and a nitrogen compound, and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, or the like, or such a functional group Since high heat resistance, light resistance, and solvent resistance can be provided by salt-formation using the resin component which has, and setting it as the salt-formation compound of an acid dye, it is preferable. Acid dyes can impart high heat resistance, light resistance and solvent resistance even by sulfonamidation.

Further, a salt-formation compound of an acid dye and a compound having an onium salt group may be used. Among them, the compound having an onium salt group is a resin having a cationic group in the side chain, and a coloring composition having excellent brightness and resistance can be obtained.

As the primary amine compound, methylamine, ethyl amine, propyl amine, isopropyl amine, butyl amine, amyl amine, hexyl amine, heptyl amine, octyl amine, nonyl amine, decyl amine, undecyl amine, dodecyl amine (lauryl amine), tridodecyl amine, tetradecyl amine (myristyl amine), pentadecyl amine, cetyl amine, stearyl amine, oleyl amine, cocoalkyl amine, tallow alkyl amine, hydrogenated tallow alkyl amine, allyl and aliphatic unsaturated primary amines such as amines, aniline, and benzyl amines.

As the secondary amine compound, aliphatically unsaturated secondary amines such as dimethyl amine, diethyl amine, dipropyl amine, diisopropyl amine, dibutyl amine, diamyl amine, and diallyl amine, methylaniline, ethylaniline, and dibenzyl amine , diphenyl amine, dicocoalkyl amine, dicured beef tallow alkyl amine, distearyl amine and the like.

Examples of the tertiary amine compound include trimethyl amine, triethyl amine, tripropyl amine, tributyl amine, triamyl amine, dimethyl aniline, diethyl aniline, and tribenzyl amine.

(quaternary ammonium salt compound)

When the organic dye used in the embodiment of the present invention is an acid dye, it is preferably used as a salt-formation compound (a) composed of an acid dye and a quaternary ammonium salt compound.

A quaternary ammonium salt compound as a counter component of an acid dye is described. A quaternary ammonium salt compound becomes a counter of acid dye by having an amino group.

A preferable form of the quaternary ammonium salt compound, which is a counter component of the salt-formation compound (a), is colorless or white. Here, colorless or white means a so-called transparent state, and is defined as a state in which transmittance is 95% or more, preferably 98% or more, in the visible light region of 400 to 700 nm in the full wave region. That is, it is preferable not to inhibit color development of the dye component and not to cause color change.

It is preferable that the range of the molecular weight of the counter part which is a cationic component of a quaternary ammonium salt compound is 190-900. Here, the cation moiety corresponds to (NR ₁ R ₂ R ₃ R ₄ ) ⁺ one moiety in the following general formula (1). When the molecular weight is smaller than 190, the light resistance and heat resistance may decrease, and the solubility to the solvent may also decrease. In addition, when the molecular weight exceeds 900, the ratio of the color developing component in the molecule decreases, and the color developing property and brightness may also decrease. More preferably, the molecular weight of the counter part is in the range of 240 to 850. Particularly preferably, the molecular weight of the counter portion is in the range of 350 to 800. Here, the molecular weight was calculated based on the structural formula, and the atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

As the quaternary ammonium salt compound, one represented by the following general formula (1) can be used.

Formula (1)

[Tuesday 4]

(In general formula (1), R ₁ to R ₄ each independently represent an alkyl group having 1 to 20 carbon atoms or a benzyl group, and at least two of R ₁ , R ₂ , R ₃ , and R ₄ are C numbers 5 to 20. Y ^- represents m inorganic or organic anion.)

By setting the number of at least two or more C's in R ₁ to R ₄ to 5 to 20, the solubility to the solvent becomes good. When the number of C alkyl groups smaller than 5 is 3 or more, the solubility in the solvent deteriorates, and foreign matter in the coating film is likely to occur. In addition, if an alkyl group in which the number of C's exceeds 20 is present, the color developing property of the salt-formation compound (a) is impaired.

The Y- component constituting the anion may be an inorganic or organic anion, but is preferably a halogen, and is usually chlorine.

As the quaternary ammonium salt compound, tetramethyl ammonium chloride, tetraethyl ammonium chloride, monostearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, tristearyl monomethyl ammonium chloride, cetyltrimethyl ammonium chloride, trioctylmethyl ammonium chloride, di Octyldimethyl ammonium chloride, monolauryltrimethyl ammonium chloride, dilauryldimethyl ammonium chloride, trilaurylmethyl ammonium chloride, triamylbenzyl ammonium chloride, trihexylbenzyl ammonium chloride, trioctylbenzyl ammonium chloride, trilaurylbenzyl ammonium chloride, benzyldimethylstearyl ammonium chloride, benzyldimethyloctyl ammonium chloride, dialkyl (alkyl is C14 to C18) dimethyl ammonium chloride (hardened beef tallow), and the like.

Specific quaternary ammonium salt compound products include, for example, QUARTAMIN 24 P, QUARTAMIN 86P conc, QUARTAMIN 60 W, QUARTAMIN 86 W, QUARTAMIN D86P, SANISOL C, SANISOL B-50, etc., manufactured by Kao Corporation, ARQUAD 210 manufactured by Lion Corporation. -80 E, 2 C-75, 2 HT-75, 2 HT flakes, 2 O-75 I, 2 HP-75, 2 HP flakes and the like, among which QUARTAMIN D86P (distearyl dimethyl ammonium chloride) , ARQUAD 2 HT-75 (dialkyl (alkyl is C14-C18) dimethyl ammonium chloride).

(Resin having a cationic group in the side chain)

When the organic dye used in the embodiment of the present invention is an acid dye, it is also preferable to use it as a salt-formation compound (a') composed of an acid dye and a resin having a cationic group in its side chain. Resin which has a cationic group in the side chain for obtaining the salt-formation compound (a') used for embodiment of this invention is demonstrated.

The resin having a cationic group in the side chain for obtaining the salt-formation compound is not particularly limited as long as it has at least one onium salt group in the side chain, but a suitable onium salt structure is ammonium salt, iodonium salt, sulfo It is preferable that they are a nium salt, a diazonium salt, and a phosphonium salt, and considering storage stability (heat resistance), it is more preferable that they are an ammonium salt, an iodonium salt, and a sulfonium salt. More preferably, it is an ammonium salt.

When preparing the blue coloring composition for color filters containing a salt-formation compound (a') and expressing the characteristics as a color filter, it is preferable to use the same type of resin as the binder resin constituting the blue coloring composition for color filters. . In one embodiment of the present invention, since acrylic resin is preferably used as binder resin in the coloring composition for color filters, resin having a cationic group in the side chain for obtaining salt-formation compound (a') is preferably acrylic resin.

As the resin having a cationic group in the side chain, an alkali resin containing a structural unit represented by the following general formula (2) can be used. A salt-formation compound can be obtained by salt-forming the cationic group in General formula (2) with the anionic group of a xanthene type acid dye.

Formula (2)

[Tuesday 5]

[In Formula (2), R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁵² to R ⁵⁴ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and two of R ⁵² to R ⁵⁴ combine with each other to form a ring; also good Q represents an alkylene group, an arylene group, -CONH-R ⁵⁵ -, or -COO-R ⁵⁵ -, and R ⁵⁵ represents an alkylene group. Y ^- represents an inorganic or organic anion.]

Examples of the alkyl group for R ⁵¹ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. As said alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

When the alkyl group represented by R ⁵¹ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

Among the above, as R ⁵¹ , a hydrogen atom or a methyl group is most preferable.

The alkyl group in R ⁵² to R ⁵⁴ is, for example, a straight-chain alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl , n-hexadecyl and n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1, 1,3,3-tetramethylbutyl, etc.), cycloalkyl groups (such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl), and bridged cyclic alkyl groups (such as norbornyl, adamantyl, and pinanyl). As said alkyl group, a C1-C18 alkyl group is preferable, More preferably, it is a C1-C8 alkyl group.

The alkenyl group in R ⁵² to R ⁵⁴ is, for example, a straight-chain or branched alkenyl group (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl , 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-pronyl, etc.), cycloalkenyl groups (2-cyclohexenyl and 3 -cyclohexenyl, etc.). As said alkenyl group, a C2-C18 alkenyl group is preferable, More preferably, it is a C2-C8 alkenyl group.

The aryl group in R ⁵² to R ⁵⁴ is, for example, a monocyclic aryl group (such as phenyl), a condensed polycyclic aryl group (naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphtho quinyl). olyl, etc.) and aromatic heterocyclic hydrocarbon groups (thienyl (group derived from thiophene), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (group derived from xanthone) and 9-oxothioxanthenyl (group derived from thioxanthone), etc.).

When the alkyl group, alkenyl group, or aryl group represented by R ⁵² to R ⁵⁴ has a substituent, the substituent is, for example, a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, a carboxy group, and a substituent selected from a phenyl group and the like. As said substituent, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are especially preferable.

As R ⁵² to R ⁵⁴ , from the viewpoint of stability, an optionally substituted alkyl group is preferable, and an unsubstituted alkyl group is more preferable.

In addition, two of R ⁵² to R ⁵⁴ may combine with each other to form a ring.

In the general formula (2), the component Q connecting the vinyl moiety and the ammonium salt group represents an alkylene group, an arylene group, -CONH-R ⁵⁵ -, -COO-R ^55- , and R ⁵⁵ represents an alkylene group. Among them, -CONH-R ^{55 -} and -COO-R ⁵⁵ - are preferable from the viewpoint of polymerizability and availability. Further, R ⁵⁵ is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

The component of Y ^- in the general formula (2) constituting the counter anion of the resin may be an inorganic or organic anion. As the counter anion, known ones can be employed without limitation, and specifically, hydroxide ions; halogen ions such as chloride ions, bromide ions, and iodide ions; carboxylate ions such as formate ions and acetate ions; carbonate ions , bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, nichromate ions, phosphate ions, cyanide ions, permanganate ions, and complex ions such as hexacyanoferric (III) acid ions. . From the viewpoint of synthesis suitability and stability, halogen ions and carboxylic acid ions are preferred, and halogen ions are most preferred. When the counter anion is an organic acid ion such as a carboxylic acid ion, the organic acid ion may be covalently bonded in the resin to form an intramolecular salt.

One method of introducing an oxetane group into a resin having a cationic group in its side chain is to copolymerize an ethylenically unsaturated monomer containing an oxetane structure with an ethylenically unsaturated monomer corresponding to the cationic group represented by the general formula (2). way.

As the ethylenically unsaturated monomer having an oxetane group, (3-methyl-3-oxetanyl) methyl (meth)acrylate, (3-ethyl-3-oxetanyl) methyl (meth)acrylate, (3-butyl -3-oxetanyl) methyl (meth)acrylate, (3-hexyl-3-oxetanyl) methyl (meth)acrylate, etc. are mentioned.

Commercially available products include, for example, ETERNACOLL OXMA (manufactured by UBE INDUSTRIES, LTD.), OXE-10, and OXE-30 (above, manufactured by OSAKA ORGANIC CHEMICAL IND. LTD.).

(salt formation)

A nitrogen compound containing an acid dye or a salt forming compound of a resin having a cationic group in a side chain can be prepared by conventionally known methods. A specific method is disclosed in Japanese Unexamined Patent Publication No. 11-72969 or the like.

For example, using a xanthene acid dye, after dissolving the xanthene acid dye in water, a quaternary ammonium salt compound may be added and a salt forming treatment may be performed while stirring. Here, a salt-formation compound in which the sulfonic acid group (-SO ₃ H) or sodium sulfonate group (-SO ₃ Na) part of the xanthene acid dye and the ammonium group (NH ₄ ⁺ ) part of the quaternary ammonium salt compound are bonded is obtained. In addition, instead of water, methanol and ethanol are solvents that can be used during salt formation.

In addition, the salt-formation compound is obtained by stirring or vibrating an aqueous solution in which a resin having a cationic group in the side chain represented by the general formula (2) and an acid dye are dissolved, or by stirring or vibrating the resin having a cationic group in the side chain represented by the general formula (2). It can be easily obtained by mixing the aqueous solution and the aqueous solution of the acid dye under stirring or vibration. In an aqueous solution, the ammonium group of the resin and the anionic group of the acid dye are ionized and these ionically bond, and the ionically bonded portion becomes water insoluble and precipitates. Conversely, since the salt composed of the counter anion of the resin and the counter cation of the acid dye is water-soluble, it can be removed by washing with water or the like. As for the resin having a cationic group in the side chain to be used and the acid dye, a single type may be used, or a plurality of types having different structures may be used.

Also, for other acid dyes, a nitrogen-containing compound or a salt forming compound with a resin having a cationic group in a side chain can be obtained by the same method as for xanthene dyes.

(sulfonic acid amide compound)

The acidic dye may be a sulfonic acid amide compound obtained by reacting a sulfonic acid amide compound with an anionic dye.

A sulfonic acid amide compound of an acid dye that can be preferably used for an acid dye is obtained by chlorination of an acid dye having -SO ₃ H and -SO ₃ Na by a conventional method, and converting -SO ₃ H to -SO ₂ Cl, This compound can be produced by reacting with an amine having a -NH ₂ group.

In addition, as an amine compound that can be preferably used for sulfonamidation, specifically, 2-ethylhexyl amine, dodecyl amine, 3-decyloxypropyl amine, 3-(2-ethylhexyloxy)propyl amine, It is preferable to use 3-ethoxypropyl amine, cyclohexyl amine or the like.

For example, in the case of obtaining a sulfonic acid amide compound obtained by modifying C.I. Acid Red 289 with 3-(2-ethylhexyloxy) propylamine using a xanthene acid dye, C.I. Acid Red 289 is sulfonylchloro After lead formation, it may be reacted with a theoretical equivalent of 3-(2-ethylhexyloxy)propylamine in dioxane to obtain C.I.Acid Red 289 sulfonic acid amide compound.

In addition, in the case of obtaining a sulfonic acid amide compound obtained by modifying C.I.Acid Red 52 with 3-(2-ethylhexyloxy)propylamine, C.I.Acid Red 52 is sulfonylchloridized, and then in dioxane. A sulfonic acid amide compound of C.I. Acid Red 52 may be obtained by reaction with an equivalent amount of 3-(2-ethylhexyloxy) propyl amine.

Also, for other acid dyes, sulfonic acid amide compounds can be obtained by the same method as for xanthene dyes.

As xanthene-based dyes, Japanese Patent Laid-Open No. 2010-032999, Japanese Patent Laid-Open No. 2011-138094, Japanese Patent Laid-Open No. 2011-227313, Japanese Patent Laid-Open No. 2011-242752, Japanese Patent Laid-Open No. 2012-107192, Japanese Patent Application Laid-open No. 2013-033194, Japanese Patent Application No. 2011-71888, Japanese Patent Application No. 2013-72263, Japanese Patent Application No. 2013-81209, Japanese Patent Laid-Open No. 2014-173064, Japanese Patent Application 2013- Publication No. 53028, Japanese Patent Application Publication No. 2013-52186, Japanese Unexamined Patent Publication No. 2014-196392, Japanese Unexamined Patent Publication No. 2014-196393, Japanese Unexamined Patent Publication No. 2014-201714, Japanese Unexamined Patent Publication No. 2014-201715, Japan Known techniques described in Japanese Patent Laid-Open No. 2013-050693, Japanese Patent Laid-Open No. 2013-178478, Japanese Patent Laid-Open No. 2013-203956, International Laid-Open No. 2013/011687, etc. can be used.

In one embodiment, as the xanthene dye, C.I.Acid Red 51, C.I.Acid Red 52, C.I.Acid Red 87, C.I.Acid Red 92, C.I.Acid Red 289, C.I.Acid Red 388, Rose Bengal B, Acid Rhodamine G, C.I. Acid Violet 9 and C.I. Acid Violet 30 are preferred. Among them, C.I. Acid Red = 52, C.I. Acid Red = 87, C.I. Acid Red = 92, C.I. Acid Red = 289, and C.I. Acid Red = 388 are more preferable.

[Dipyrromethene dye]

As the dipyrromethene-based dye, it is a dye having a partial structure derived from the dipyrromethene dye as a partial structure of the dye moiety, and is a dipyrromethene compound, and a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or metal compound. This is preferable, and among these, a metal complex compound in which the structure represented by the general formula (3) is coordinated with a metal atom or a metal compound (hereinafter, appropriately referred to as "dipyrromethene metal complex compound") is preferable.

[Dipyrromethene metal complex compound]

A metal complex compound (dipyrromethene metal complex compound) in which the structure represented by the general formula (3) is coordinated to a metal atom or a metal compound will be described.

Formula (3)

[Tue 6]

In formula (3), R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.

The metal or metal compound may be any metal atom or metal compound capable of forming a complex, and includes a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, and a divalent metal chloride. Metals or metal compounds include, for example, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., as well as AlCl ₃ , InCl ₃ , FeCl ₃ , TiCl ₂ , SnCl ₂ , SiCl ₂ , GeCl ₂ and the like, metal oxides such as TiO and VO, and metal hydroxides such as Si(OH) ₂ are also included.

Among these, as a metal or metal compound, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO is preferred, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferred, and Fe, Zn, Cu, Co, B, or VO is most desirable

As such dipyrromethene-based dyes, Japanese Patent Laid-Open No. 2008-292970, Japanese Patent Laid-Open No. 2010-85758, Japanese Patent Laid-Open No. 2010-84009, Japanese Patent Application No. 2010-43530, and Japanese Patent Laid-Open No. 2013-080010 Publication, Japanese Unexamined Patent Publication No. 2013-210596, International Publication No. 2013/141156, a pamphlet, etc. can be used.

[Triphenylmethane dye]

Examples of the triphenylmethane-based dye skeleton include a diaminotriphenylmethane-based dye skeleton, a triaminotriphenylmethane-based dye skeleton, and a rosolic acid-based dye skeleton having an OH group.

The triaminotriphenylmethane-based dye backbone is preferable in that it has excellent color tone and superior light fastness to others. Among them, diphenyl naphthyl methane dye skeletons, which are basic dyes, are particularly preferred.

[triphenylmethane basic dye]

Triphenylmethane-based basic dyes develop color when an NH ₂ or OH group at a para position with respect to a central carbon is oxidized to form a quinone structure.

It can be divided into the following three forms according to the number of NH ₂ and OH groups, but among them, the form of a triaminoaryl methane-based basic dye is preferable in terms of developing good blue, red, and green colors.

a) Diaminotriphenylmethane-based basic dye

b) Triaminotriphenylmethane-based basic dye

c) Rosolic acid-based basic dyes having an OH group

Triaminotriphenylmethane-based basic dyes and diaminotriphenylmethane-based basic dyes are preferred because they have vivid colors and superior light fastness to others.

Blue-based triphenylmethane-based basic dyes have spectral characteristics with high transmittance at 400 to 440 nm, and are therefore preferable because they can achieve high brightness when used for forming a blue filter segment.

Specifically as triphenylmethane-based basic dyes, C.I.BASIC Violet 1 (methyl violet), C.I.BASIC Violet 3 (crystal violet), C.I.BASIC Violet 14 (magenta), C.I.BASIC Blue 1 (basic cyanine 6 G), C.I.BASIC Blue 5 (Basic Cyanine EX), C.I.BASIC Blue 7 (Victoria Pure Blue BO), C.I.BASIC Blue 26 (Victoria Blue 　 Bconc.), C.I.BASIC Green 1 (Brilliant Green GX), C.I.BASIC Green 4 (Malachite Green), etc. can be heard

Among them, it is preferable to use C.I.BASIC Blue 7 from the point of lightness.

In addition, in the case of a triphenyl-based basic dye, it can be used by forming a salt using an organic acid, perchloric acid, or a metal salt thereof. Among them, salt-formation compounds of basic dyes are preferable because they are excellent in resistance and compatibility with pigments, and are organic sulfonic acids, organic sulfuric acids, fluorine group-containing phosphorus anion compounds that are counter components that act as counter ions with basic dyes, It is more preferable to use a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugated base of an organic acid having a halogenated hydrocarbon group, or a salt-formation compound obtained by forming a salt with an acidic dye.

Specifically, organic acids such as heteropolyacids, organic sulfonic acids such as aliphatic sulfonic acids and aromatic sulfonic acids, organic sulfuric acids such as aliphatic sulfuric acids and aromatic sulfuric acids, organic carboxylic acids such as aromatic carboxylic acids and fatty acids, or acidic dyes will have the form of Or these metal salts may be sufficient. Moreover, the salt-formation compound with resin which has an acidic group is also preferable.

(salt formation)

A salt-formation compound of such a basic dye and anionic counter can be synthesized by a conventionally known method. A specific method is disclosed in Japanese Patent Application Laid-Open No. 2003-215850 or the like.

For example, after dissolving a triarylmethane-based basic dye in water, a salt-forming treatment may be performed while adding and stirring an organic sulfonic acid or (sodium organic sulfonate) solution. Here, a salt-forming compound in which the amino group (-NHC ₂ H ₅ ) part of the triaryl methane-based basic dye and the sulfonic acid group (-SO ₃ H) part of the organic sulfonic acid are bonded is obtained.

Here, the organic sulfonic acid may be dissolved in an alkali solution such as sodium hydroxide before performing a salt-forming treatment, and used in the form of sodium sulfonate (-SO ₃ Na). In the present disclosure, a sulfonic acid group (-SO ₃ H) and a functional group that is sodium sulfonate (-SO ₃ Na) may be referred to without distinction.

As such a triphenylmethane-based dye, Japanese Unexamined Patent Publication No. 2002-014222, Japanese Unexamined Patent Publication No. 2003-246935, Japanese Unexamined Patent Publication No. 2003-246935, Japanese Unexamined Patent Publication No. 2008-304766, Japanese Unexamined Patent Publication 2010-256598 Japanese Patent Application Publication No. 2011-200560, Japanese Patent Application Laid-Open No. 2011-186043, Japanese Patent Laid-Open No. 2012-173399, Japanese Patent Laid-Open No. 2012-233033, Japanese Patent Laid-Open No. 2012-098522, Japanese Patent Application No. 2012-288970, Japanese Patent Application No. 2012-200469, Japanese Patent Application No. 2014-196262, International Publication No. 2010/123071 Pamphlet, International Publication No. 2011/162217 Pamphlet, International Publication No. 2013/108591 A known technique described in a pamphlet or the like can be used.

In one embodiment, as the triphenylmethane dye, C.I.Acid Violet 15, C.I.Acid Violet 17, C.I.Acid Violet 19, C.I.Acid Violet 21, C.I.Acid Violet 24, C.I.Acid Violet 25, C.I.Acid Violet 38, C.I.Acid Violet olet 49, C.I.Acid Blue=1, C.I.Acid Blue=3, C.I.Acid Blue=5, C.I.Acid Blue=7, C.I.Acid Blue=9, C.I.Acid Blue=11, C.I.Acid Blue=13, C.I.Acid Blue=15, C.I.Acid Blue=17, C.I.Acid Blue 22, C.I.Acid Blue 24, C.I.Acid Blue 26, C.I.Acid Blue 75, C.I.Acid Blue 83, C.I.Acid Blue 90, C.I.Acid Blue 93, C.I.Acid Blue 100, C.I.BASIC Blue 81, C.I.BASIC Blue 8 It is preferable to use 3 do.

Alternatively, C.I.BASIC Violet 1, C.I.BASIC Violet 2, C.I.BASIC Violet 3, C.I.BASIC Violet 4, C.I.BASIC Violet 14, C.I.BASIC Blue 1, C.I.BASIC Blue 5, C.I.BASIC Blue 7, C.I.BASIC as triarylmethane dyes Blue 11, C.I.BASIC Blue 26 can be preferably used.

[Cyanine dye]

As the cyanine-based dye, any compound having a dye moiety containing a cyanine backbone in the molecule can be used without limitation.

Cyanine dyes include, for example, C.I.BASIC Yellow 11, 12, 13, 14, 21, 22, 23, 24, 28, 29, 33, 35, 40, 43, 44, 45, 48, 49, 51, 52 , 53, C.I.BASIC Red 12, 13, 14, 15, 27, 35, 36, 37, 45, 48, 49, 52, 53, 66, 68, C.I.BASIC Violet 7, 15, 16, 20, 21, 39 , 40, C.I.BASIC Orange 27, 42, 44, 46, C.I.BASIC Blue 62, 63 and the like.

In addition, cyanine-based dyes described in Japanese Unexamined Patent Publication No. 2014-224970, Japanese Unexamined Patent Publication No. 2013-261614, etc. can also be used.

[Anthraquinone dyes]

An anthraquinone dye is a dye having an anthraquinone skeleton in a molecule.

Anthraquinone dyes are, for example, C.I. Solvent Yellow 117, 163, 167, 189, C.I. Solvent Orange 77, 86, C.I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, C.I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, C.I.Solvent Green 3, 28, 29, 32, 33, C.I.Acid Red 80, C.I.Acid Green 25, 27, 28, 41, C.I.Acid Violet 34, C.I.Acid Blue 25, 27 , 40, 45, 78, 80, 112, C.I.Disperse Yellow 51, C.I.Disperse Violet 26, 27, C.I.Disperse Blue 1, 14, 56, 60, C.I.Direct Blue 40, C.I.Mordant Red 3, 11, C.I.Mordant Blue 8 etc. can be mentioned. In addition, Japanese Patent Laid-Open No. 9-291237, International Publication No. 2003/080734 Pamphlet, International Publication No. 2006/024617 Pamphlet, Japanese Patent Laid-Open No. 2011-174987, Japanese Unexamined Patent Publication No. 2013-53273, etc. Anthraquinone dyes can be used as a known technique. The anthraquinone dye is preferably dissolved in an organic solvent, and a blue, violet or red anthraquinone dye is more preferable. As anthraquinone dyes, C.I. Solvent Blue 35, C.I. Solvent Blue 45, C.I. Acid Blue 80, C.I. Solvent Blue 104, and C.I. Solvent Blue 122 are preferable from the viewpoint of brightness or contrast.

In one embodiment, C.I.Acid Violet 29, C.I.Acid Violet 31, C.I.Acid Violet 33, C.I.Acid Violet 34, C.I.Acid Violet 36, C.I.Acid Violet 39, C.I.Acid Violet 43, C.I.Acid as the anthraquinone dye. id Violet　48, C.I.Acid Violet=63, C.I.Acid Violet=109, C.I.Acid Blue=25, C.I.Acid Blue=27, C.I.Acid Blue=41, C.I.Acid Blue=45, C.I.Acid Blue=62, C.I.Acid Blue=80, C.I.Acid Blue=127 , C.I. Acid Blue 129, C.I.Acid Blue=145, C.I.Acid Blue=225, C.I.Acid Blue=230, C.I.Acid Blue=260, C.I.Acid Blue=264, C.I.Acid Blue=277, C.I.Acid Blue=281, C.I.Acid Blue=324, or C.I.Acid Blue It is preferable to use 　350 .

In order to improve the color reproduction characteristics of recent color filters and reduce their thickness, it is necessary to increase the content of the colorant in the photosensitive coloring composition. The content of the coloring agent (A) is preferably 30% by mass or more, more preferably 40% by mass or more, based on 100 parts by mass of the non-volatile matter of the photosensitive coloring composition for color filters according to the embodiment of the present invention, to achieve sufficient color reproducibility. This is preferable because it can be obtained and the film thickness is reduced. Moreover, if it is preferably 65% by mass or less, more preferably 60% by mass or less, the content of the resin or photopolymerizable compound as the curing material becomes appropriate, and a sufficient cured coating film can be obtained. In general, when the content of the colorant increases, the patterning properties of the photosensitive coloring composition tend to deteriorate. According to the present invention, not only the photosensitive coloring composition in which the content of the colorant required for general high color reproduction is from 30% by mass to less than 40% by mass, but also in the photosensitive coloring composition in which the content of the colorant with a higher degree of difficulty is 40% by mass or more. Sufficient patterning characteristics can also be obtained.

<Photoinitiator (C)>

The photosensitive composition of the present invention is prepared in the form of a solvent developing type or alkali developing type photosensitive composition by adding a photopolymerization initiator (C) in order to cure the composition by ultraviolet irradiation and form a filter segment by photolithography. it is essential As for the compounding quantity of a photoinitiator, it is more preferable that it is 0.3-8.0 mass % in total non-volatile matter of a photosensitive coloring composition from a viewpoint of a practical ultraviolet sensitivity.

As the photopolymerization initiator (C), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane- 1-one, 1-hydroxycyclohexyl phenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[ (4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane Acetophenone-based compounds such as -1-one; Benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3, 3', 4, 4'-tetra(t-butylperoxycarbonyl) benzo Benzophenone compounds such as phenone; Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropyl thioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethyl Thioxanthone-based compounds such as thioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methyl); Toxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-piperonyl - 4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphtho-1-yl)-4, 6-bis(trichloromethyl)-s-triazine, 2,4- Triazine compounds such as trichloromethyl-(piperonyl)-6-triazine or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2-octanedione , 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- yl] -, 1-(O-acetyl oxime) and other oxime ester compounds; bis(2,4,6-trimethylbenzoyl) phenylphosphine oxide, or 2,4,6-trimethylbenzoyl diphenylphosphine oxide, etc. phosphine-based compounds; quinone-based compounds such as 9,10-phenanthrene quinone, compar-quinone, and ethyl anthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; or titanocene-based compounds; . These photoinitiators can be used individually or in combination of 2 or more types.

As a commercial item, as an acetophenone compound, "IRGACURE 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), "IRGACURE 369" all manufactured by BASF. (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), "IRGACURE 379" 2-benzyl-2- As dimethylamino-1-(4-morpholinophenyl)-butan-1-one and phosphine compounds, all are BASF's "IRGACURE 819" (bis(2,4,6-trimethylbenzoyl) phenylphosphine oxide) , "IRGACURE TPO" (2, 4, 6-trimethylbenzoyl diphenylphosphine oxide), etc. are mentioned. Among these, an oxime ester type compound is preferable.

[Oxime ester compound]

In the oxime ester-based compound, dissociation of the N-O bond of the oxime occurs by absorbing ultraviolet rays to generate an iminyl radical and an alkyloxy radical. Since these radicals further decompose to generate highly active radicals, patterns can be formed with a small exposure amount. The oxime ester-based compound is preferably an oxime ester-based photopolymerization initiator represented by general formula (4). By using the above initiator, the resin type dispersant (B) can be efficiently polymerized.

(Oxime ester photopolymerization initiator represented by general formula (4))

Formula (4)

[Tue 7]

In formula (4),

Y ¹ is a hydrogen atom or an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, which may have a substituent; an arylsulfinyl group, an alkylsulfonyl group, an aryl sulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group;

Y ² is a hydrogen atom or an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, which may have a substituent; An aryl sulfinyl group, an alkyl sulfonyl group, an aryl sulfonyl group, an acyloxy group, or an amino group.

Z is a direct bond or a -CO- group;

Y ³ is preferably a monovalent organic group containing a carbazole group which may have a substituent, or a Ph-S-Ph- group (Ph represents a phenyl group or phenylene group which may have a substituent).

Examples of the alkenyl group which may have a substituent in Y ¹ include linear, branched, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms, and these have a plurality of carbon-carbon double bonds in their structures. may be present, and specific examples include a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadiene A yl group, a cyclohexadienyl group, a cyclopentadienyl group, etc. are mentioned.

As an alkyl group which may have a substituent in Y ¹ , a straight-chain, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or a C 2 to 18 alkyl group, optionally interrupted by one or more -O- linear, branched, monocyclic or condensed polycyclic alkyl groups. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. , dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclo A propyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, 4-decylcyclohexyl group, etc. are mentioned. Further, as specific examples of a straight-chain or branched-chain alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of -O-, -CCH _2- O-CH ₃ , -CCH _2- CH _2- O -ＣＨ _２- ＣＨ _３ , -ＣＨ _２- ＣＨ _２- ＣＨ _２- Ｏ-ＣＨ _２ -ＣＨ _３ , -（ＣＨ _{２ -ＣＨ ２ -} O） _n -ＣＨ _３ (where n is 1 to 8), - (ＣＨ _２ -ＣＨ _２- ＣＨ _２- Ｏ) _m -ＣＨ _３ (where m is 1 to 5), -ＣＨ _{２ -ＣＨ} （ＣＨ _３ ）-Ｏ-ＣＨ _２- ＣＨ _３ -, -ＣＨ _２ -CHS -（ＯＣＨ _３ ） _２ etc.

Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms, optionally interrupted by one or more -O-, include, but are not limited to, the following.

[Tue 8]

As an alkyloxy group which may have a substituent in Y ¹ , a straight-chain, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or a C 2 to 18 alkyloxy group, optionally containing one or more - A straight-chain, branched-chain, monocyclic or condensed polycyclic alkyloxy group interrupted by O- is exemplified. Specific examples of the straight-chain, branched-chain, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms include a methyloxy group, an ethyloxy group, a propyloxy group, a butyloxy group, a pentyloxy group, a hexyloxy group, Heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group period, sec-pentyloxy group, tert-pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decylcyclohexyloxy group, etc. are mentioned. Further, as specific examples of the straight-chain or branched-chain alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more -O-, -O-CCH _2- OCH ₃ , -OCH _2- ＣＨ _２- Ｏ-ＣＨ _２- ＣＨ _３ , -Ｏ-ＣＨ _２- ＣＨ _２- ＣＨ _２- Ｏ-ＣＨ _２- ＣＨ _３ , -Ｏ-（ＣＨ _２- ＣＨ _２- Ｏ） _n- ＣＨ _３ (here n is 1 to 8), -Ｏ-（ＣＨ _２- ＣＨ _２- ＣＨ _２- Ｏ） _m- ＣＨ _３ (where m is 1 to 5), -Ｏ-ＣＨ _２- ＣＨ（ＣＨ _３ ）-Ｏ- ＣＨ _２- ＣＨ _３- , -Ｏ-ＣＨ _２- ＣＨ-（ＯＣＨ _３ ） _２ etc. are mentioned.

Specific examples of the monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms, optionally interrupted by one or more -O-, include, but are not limited to, the following.

[Tue 9]

Examples of the aryl group which may have a substituent in Y ¹ include monocyclic or condensed polycyclic aryl groups having 6 to 24 carbon atoms, and specific examples include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 9- Anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesh ethyl group, p-cumenyl group, p-dodecyl phenyl group, p-cyclohexyl phenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group, m-carboxy A phenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azide phenyl group, etc. are mentioned.

Examples of the aryloxy group which may have a substituent in Y ¹ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms, and specific examples thereof include a phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, and 9-annular Triloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group etc. can be mentioned.

As the heterocyclic group which may have a substituent in Y ¹ , an aromatic or aliphatic heterocyclic group having 4 to 24 carbon atoms containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom is exemplified, and 2-thienyl group and 2-benzo Thienyl group, naphtho [2,3-b] thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl group, chromenyl group, Xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolidinyl group, isoindolyl group, 3 H-indolyl group, 2-indolyl group, 3-indolyl group, 1 H-indazolyl group, purinyl group, 4 H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, Naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cynnolinyl group, pteridinyl group, 4 aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbonyl group, Phenantridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenarsazinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group , 3-phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, pipera Zinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxa A thienyl group, 3-coumarinyl group, etc. are mentioned.

Examples of the heterocyclic oxy group which may have a substituent in Y ¹ include a monocyclic or condensed polycyclic heterocyclic oxy group containing a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom and having 4 to 18 carbon atoms. Specific examples include 2 -Furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group, 3-carboxy group A bazolyloxy group, 4-carbazolyloxy group, 9-acridinyloxy group, etc. are mentioned.

Examples of the alkylsulfanyl group which may have a substituent in Y ¹ include straight chain, branched, monocyclic or condensed polycyclic alkylthio groups having 1 to 18 carbon atoms, and specific examples thereof include methylthio groups, ethylthio groups, and propyl groups. A thio group, a butyl thio group, a pentyl thio group, a hexyl thio group, an octyl thio group, a decyl thio group, a dodecyl thio group, an octadecyl thio group, etc. are mentioned.

Examples of the arylsulfanyl group which may have a substituent in Y ¹ include monocyclic or condensed polycyclic arylthio groups having 6 to 18 carbon atoms, and specific examples include phenylthio groups, 1-naphthylthio groups, and 2-naphthylthio groups. Ogi, 9-anthryl thio group, 9-phenanthryl thio group, etc. are mentioned.

As the alkyl sulfinyl group which may have a substituent in Y ¹ , an alkyl sulfinyl group having 1 to 20 carbon atoms is preferable. Hexyl sulfinyl group, cyclohexyl sulfinyl group, octyl sulfinyl group, 2-ethylhexyl sulfinyl group, decanoyl sulfinyl group, dodecanoyl sulfinyl group, octadecanoyl sulfinyl group, cyanomethyl sulfinyl group, methyloxymethyl sulfinyl group, etc. can be heard

As the aryl sulfinyl group which may have a substituent in Y ¹ , an aryl sulfinyl group having 6 to 30 carbon atoms is preferable, and specific examples include phenyl sulfinyl group, 1-naphthyl sulfinyl group, 2-naphthyl sulfinyl group, and 2-chloro phenyl sulfinyl group, 2-methylphenyl sulfinyl group, 2-methyloxyphenyl sulfinyl group, 2-butyloxyphenyl sulfinyl group, 3-chlorophenyl sulfinyl group, 3-trifluoromethylphenyl sulfinyl group, 3-cyanophenyl sulfinyl group, 3-nitrophenyl sulfinyl group, 4-fluorophenyl sulfinyl group, 4-cyanophenyl sulfinyl group, 4-methyloxyphenyl sulfinyl group, 4-methylsulfanylphenyl sulfinyl group, 4-phenylsulfanylphenyl sulfinyl group, 4 - A dimethylaminophenyl sulfinyl group etc. are mentioned.

As the alkyl sulfonyl group which may have a substituent in Y ¹ , an alkyl sulfonyl group having 1 to 20 carbon atoms is preferable, and specific examples thereof include methyl sulfonyl group, ethyl sulfonyl group, propyl sulfonyl group, isopropyl sulfonyl group, butyl sulfonyl group Hexyl sulfonyl group, cyclohexyl sulfonyl group, octyl sulfonyl group, 2-ethylhexyl sulfonyl group, decanoyl sulfonyl group, dodecanoyl sulfonyl group, octadecanoyl sulfonyl group, cyanomethyl sulfonyl group, methyloxymethyl sulfonyl group, etc. can be heard

As the aryl sulfonyl group which may have a substituent in Y ¹ , an aryl sulfonyl group having 6 to 30 carbon atoms is preferable, and specific examples include a phenyl sulfonyl group, 1-naphthyl sulfonyl group, 2-naphthyl sulfonyl group, and 2-chloro phenyl sulfonyl group, 2-methylphenyl sulfonyl group, 2-methyloxyphenyl sulfonyl group, 2-butyloxyphenyl sulfonyl group, 3-chlorophenyl sulfonyl group, 3-trifluoromethylphenyl sulfonyl group, 3-cyanophenyl sulfonyl group, 3-nitrophenyl sulfonyl group, 4-fluorophenyl sulfonyl group, 4-cyanophenyl sulfonyl group, 4-methyloxyphenyl sulfonyl group, 4-methylsulfanylphenyl sulfonyl group, 4-phenylsulfanylphenyl sulfonyl group, 4 - A dimethylaminophenyl sulfonyl group etc. are mentioned.

As an acyl group which may have a substituent in Y ¹ , a carbonyl group in which a carbon atom or a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or an alkyloxy group having 2 to 20 carbon atoms is substituted. A carbonyl group, a carbonyl group bonded to a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms, a carbonyl group substituted with a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Examples include a carbonyl group to which a monocyclic or fused polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, and specific examples include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, and pivalyl groups. , lauroyl group, myristoyl group, palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonyl group, isocrotonoyl group, oleoyl group, cinnamoyl group , Benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyleneoxycarbonyl group, butyloxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoyl group , 1-naphthoyl group, 2-naphthoyl group, 9-anthrylcarbonyl group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 2-methylsulfanylphenyl An oxycarbonyl group, 1-naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-antryloxycarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, isonicotinoyl group, etc. are mentioned.

Examples of the acyloxy group that may have a substituent in Y ¹ include an acyloxy group having 2 to 20 carbon atoms, and specific examples include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, and a trifluoromethylcarboxy group. A bornyloxy group, a benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group, etc. are mentioned.

Examples of the amino group that may have a substituent in Y ¹ include an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, and a dibenzylamino group.

Here, as the alkylamino group, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group, octadecylamino group, isopropylamino group, isobutyl Amino group, isopentyl amino group, sec-butylamino group, tert-butylamino group, sec-pentyl amino group, tert-pentyl amino group, tert-octyl amino group, neopentyl amino group, cyclopropyl amino group, cyclobutyl amino group, cyclopentyl amino group, cyclohexyl amino group , cycloheptyl amino group, cyclooctyl amino group, cyclododecyl amino group, 1-adamantamino group, 2-adamantamino group and the like.

Examples of the dialkylamino group include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutyl amino group, a dipentylamino group, a dihexylamino group, a diheptylamino group, a dioctylamino group, a dinonylamino group, a didecylamino group, a didodecylamino group, and a diocta Decyl amino group, diisopropylamino group, diisobutyl amino group, diisopentylamino group, methylethylamino group, methylpropyl amino group, methylbutyl amino group, methyl isobutyl amino group, cyclopropyl amino group, pyrrolidino group, piperidino group, piperazi Nogi, etc. are mentioned.

As an arylamino group, an anilino group, 1-naphthyl amino group, 2-naphthyl amino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-bi A phenylamino group, 4-biphenylamino group, 1-fluorene amino group, 2-fluorene amino group, 2-thiazole amino group, p-terphenyl amino group, etc. are mentioned.

Examples of the diarylamino group include diphenylamino group, ditolylamino group, N-phenyl-1-naphthylamino group, and N-phenyl-2-naphthylamino group.

As the alkylarylamino group, N-methylanilino group, N-methyl-2-pyridino group, N-ethyl anilino group, N-propyl anilino group, N-butyl anilino group, N-isopropyl, N- A pentyl anilino group, N-ethyl anilino group, N-methyl-1-naphthyl amino group, etc. are mentioned.

Examples of the phosphinoyl group that may have a substituent in Y ¹ include a phosphinoyl group having 2 to 50 carbon atoms, and specific examples include a dimethylphosphinoyl group, a diethylphosphinoyl group, a dipropyl phosphinoyl group, and a diphenylphosphino group. diyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoyl phosphinoyl group, bis(2,4,6-trimethylphenyl) phosphinoyl group and the like.

Examples of the carbamoyl group that may have a substituent in Y ¹ include a carbamoyl group having 1 to 30 carbon atoms, and specific examples thereof include N-methylcarbamoyl group, N-ethyl carbamoyl group, N-propyl carbamoyl group, N-butyl carbamoyl group, N-hexyl carbamoyl group, N-cyclohexyl carbamoyl group, N-octyl carbamoyl group, N-decyl carbamoyl group, N-octadecyl carbamoyl group, N-phenyl carbamoyl group , N-2-methylphenyl carbamoyl group, N-2-chlorophenyl carbamoyl group, N-2-isopropoxyphenyl carbamoyl group, N-2-(2-ethylhexyl)phenyl carbamoyl group, N-3 -Chlorophenyl carbamoyl group, N-3-nitrophenyl carbamoyl group, N-3-cyanophenyl carbamoyl group, N-4-methoxyphenyl carbamoyl group, N-4-cyanophenyl carbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N,N-dimethylcarbamoyl group, N,N-dibutyl A carbamoyl group, a N,N-diphenyl carbamoyl group, etc. are mentioned.

Examples of the sulfamoyl group which may have a substituent in Y ¹ include a sulfamoyl group having 0 to 30 carbon atoms, and specific examples include a sulfamoyl group, an N-alkylsulfamoyl group, an N-aryl sulfamoyl group, N,N -Dialkyl sulfamoyl group, N,N-diaryl sulfamoyl group, N-alkyl-N-aryl sulfamoyl group, etc. are mentioned. More specifically, N-methyl sulfamoyl group, N-ethyl sulfamoyl group, N-propyl sulfamoyl group, N-butyl sulfamoyl group, N-hexyl sulfamoyl group, N-cyclohexyl sulfamoyl group, N- Octyl sulfamoyl group, N-2-ethylhexyl sulfamoyl group, N-decyl sulfamoyl group, N-octadecyl sulfamoyl group, N-phenyl sulfamoyl group, N-2-methylphenyl sulfamoyl group, N-2- Chlorophenyl sulfamoyl group, N-2-methoxyphenyl sulfamoyl group, N-2-isopropoxyphenyl sulfamoyl group, N-3-chlorophenyl sulfamoyl group, N-3-nitrophenyl sulfamoyl group, N -3-cyanophenyl sulfamoyl group, N-4-methoxyphenyl sulfamoyl group, N-4-cyanophenyl sulfamoyl group, N-4-dimethylaminophenyl sulfamoyl group, N-4-methylsulfanyl Phenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl group, N-methyl-N-phenylsulfamoyl group, N, N-dimethyl sulfamoyl group, N, N-dibutyl sulfamoyl group, N, N -Diphenyl sulfamoyl group etc. are mentioned.

an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, which may have a substituent in Y ² ; As the alkyl sulfonyl group, aryl sulfonyl group, acyloxy group, and amino group, the alkenyl group which may have a substituent in the aforementioned R1, the alkyl group which may have a substituent, the alkyloxy group which may have a substituent, the alkyloxy group which may have a substituent, An aryl group, an aryloxy group which may have a substituent, a heterocyclic group which may have a substituent, a heterocyclic oxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, an arylsulfanyl group which may have a substituent, a substituent An alkyl sulfinyl group which may have a substituent, an aryl sulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an aryl sulfonyl group which may have a substituent, an acyloxy group which may have a substituent, and an amino group which may have a substituent agree with

Such substituents in Y ¹ and Y ² include, for example, halogen groups such as fluorine, chlorine, bromine and iodine, alkoxy groups such as methoxy, ethoxy and tert-butoxy groups, phenoxy groups, p- aryloxy groups such as tolyloxy groups, methoxycarbonyl groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups and benzoyloxy groups, acetyl groups, benzoyl groups, iso acyl groups such as butyryl, acryloyl, methacryloyl and methoxalyl groups, alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups, arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl groups, Alkylamino groups such as methylamino group and cyclohexylamino group, dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, methyl group, ethyl group, tert-butyl group, an alkyl group such as a dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclooctadecyl group, a phenyl group, a p-tolyl group, a xylyl group, and a cumenyl group , aryl groups such as naphthyl group, anthryl group and phenanthryl group, heterocyclic groups such as furyl group and thienyl group, etc., hydroxyl group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfo Nyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumyl group, dimethylsulfoniumyl group, triphenylphenacyl A phosphonium wheat group etc. are mentioned.

In addition, one or more or more than one of these substituents may be present, and the hydrogen atom of these substituents may be further substituted with another substituent.

Among the oxime ester-based photopolymerization initiators represented by the general formula (4), the oxime ester-based photopolymerization initiators represented by the following general formula (5) or (6), particularly the oxime ester-based photopolymerization initiators represented by the general formula (6) having a carbazole moiety in the molecule. The photopolymerization initiator is the photopolymerization initiator (C) used in the present invention and is more preferable among oxime ester photopolymerization initiators in order to obtain good patterning characteristics in combination with the resin type dispersant (B).

(Oxime ester photopolymerization initiator represented by general formula (5))

Formula (5)

[Tue 10]

In general formula (5), Z in general formula (4) corresponds to the case where -CO- group, Y ³ represents Ph-S-Ph- group, Y ⁴ to Y ⁶ are hydrogen atoms or substituents. An alkyl group or an aryl group, which may be present, is preferable. The alkyl group which may have a substituent or the aryl group which may have a substituent in Y ⁴ to Y ⁶ is synonymous with the alkyl group or aryl group in Y ¹ and Y ² .

Further, Y ¹ is an aryl group which may have a substituent, Y ² is an alkyl group having 1 to 20 carbon atoms which may have a substituent, Y ⁴ and Y ⁶ are more preferably a hydrogen atom, and Y ⁵ is a hydrogen atom or Y ^7- It is more preferably a CO-group.

Y ⁷ is, for example, a halogen group such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group, an aryloxy group such as a phenoxy group and a p-tolyloxy group. groups, methoxycarbonyl groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups and benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups, Acyl groups such as methacryloyl and methoxalyl groups, alkyl sulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups, arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl groups, methylamino groups, cyclohexylamino groups, etc. Alkyl groups such as dialkylamino groups such as alkylamino groups, dimethylamino groups, diethylamino groups, morpholino groups and piperidino groups, arylamino groups such as phenylamino groups and p-tolylamino groups, methyl groups, ethyl groups, tert-butyl groups and dodecyl groups , phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, aryl groups such as benzofuranyl group, heterocyclic groups such as furyl group and thienyl group, hydroxyl group, carboxy group , formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, A trimethylanmoniumyl group, a dimethyl sulfoniumyl group, a triphenylphenacylphosphoniumyl group, etc. are mentioned.

The substituent for Y ² is more preferably a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or a cyclooctadecyl group.

Examples of the oxime ester photopolymerization initiator represented by the general formula (5) include photopolymerization initiators represented by the following chemical formulas (5-1) to (5-4).

[Tue 11]

Formula (5-1) Formula (5-2)

Chemical formula (5-3)

Chemical formula (5-4)

(Oxime ester photopolymerization initiator represented by general formula (6))

Formula (6)

[Tue 12]

In general formula (6), Y ³ in general formula (4) corresponds to the case of a monovalent organic group containing a carbazole group which may have a substituent, and Y ⁷ to Y ¹⁴ are Y ¹ and Y ² It is synonymous with the substituent in

Further, as Y ¹ , an alkyl group having 1 to 20 carbon atoms which may have a substituent, as Y ² , an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent is a hydrogen atom as Y ⁷ to Y ¹⁴ , Or a C1-C20 alkyl group which may have a substituent, or an aryl group which may have a substituent is preferable.

When Z in the general formula (6) is a direct bond, an oxime ester-based photopolymerization initiator represented by the following general formula (6a) is preferable.

(oxime ester photopolymerization initiator represented by general formula (6a))

Formula (6a)

[Tue 13]

In the general formula (6a), Z in the general formula (6) corresponds to a direct bond, and Y ⁷ to Y ¹⁰ and Y ¹² to Y ¹³ in the general formula (6) are hydrogen atoms.

Further, Y ¹¹ is preferably a Y ¹⁵ -CO- group or a nitro group. Y ¹⁵ is synonymous with the substituents in Y ¹ and Y ² , and is preferably an aryl group which may have a substituent. The Y ¹⁵ -CO- group is preferably an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, or a methoxalyl group, which may further have a substituent. More preferably, it is a benzoyl group which may have a substituent, or a nitro group. As Y ¹⁴ , an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group which may have a substituent is preferable.

Moreover, as a substituent in the benzoyl group which may have a substituent, a C1-C20 alkyl group or an alkyloxy group is preferable. As the alkyl group, a methyl group and an ethyl group are preferable. Among the alkyloxy groups, a straight-chain, branched-chain, monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and interrupted by one or more -O- as the case may be used. It is preferably synonymous with a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms in Y ¹ and optionally interrupted by one or more -O-.

Y ² is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, and the substituent is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or a cyclo They are cycloalkyl groups, such as an octadecyl group. Further, an aryl group which may have a substituent is preferable, and the substituent is preferably an alkyl group having 1 to 20 carbon atoms, or an alkoxy group such as a methoxy group, an ethoxy group, or a tert-butoxy group, which may also have a substituent.

Examples of the oxime ester photopolymerization initiator represented by the general formula (6a) include photopolymerization initiators represented by the following chemical formulas (6a-1) to (6a-6), and the like.

[Tue 14]

Chemical formula（6a-1）　 Chemical formula（6a-2）

Chemical formula (6a-3)　　　　　chemical formula (6a-4)

Chemical formula (6a-5) 　　　　　chemical formula (6a-6)

(Oxime ester photopolymerization initiator represented by general formula (6b))

When Z in the general formula (6) is a -CO- group, an oxime ester photopolymerization initiator represented by the following general formula (6b) is preferable.

Formula (6b)

[Tuesday 15]

In general formula (6b), Z is a -CO- group in general formula (6), and Y ³ corresponds to the case of a monovalent organic group containing a carbazole group which may have a substituent, and is a keto-type carbazole group. It is an oxime ester-based photopolymerization initiator having a.

Y ⁷ to Y ¹³ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and Y ¹⁴ is preferably an aryl group which may have a substituent.

As a substituent of the aryl group which may have a substituent, an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, or a methoxalyl group is preferable, and a benzoyl group is more preferable.

Examples of the oxime ester photopolymerization initiator represented by the general formula (6b) include photopolymerization initiators represented by the following chemical formulas (6b-1) to (6b-4), and the like.

[Tue 16]

Formula (6b-1) 　　　　　　　Formula (6b-2)

Chemical formula (6b-3) Chemical formula (6b-4)

Commercially available products of these oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)] (IRGACURE OXE-01), and ethanone from BASF. , 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole 3-yl]-, 1-(O-acetyl oxime) (IRGACURE OXE 02), N-1919 (manufactured by Adeka), TRONLY TR-PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (all manufactured by TRONLY) and the like are commercially available. In addition, in addition, Japanese Unexamined Patent Publication No. 2007-210991, Japanese Unexamined Patent Publication No. 2009-179619, Japanese Unexamined Patent Publication No. 2010-037223, Japanese Unexamined Patent Publication No. 2010-215575, Japanese Unexamined Patent Publication No. 2011-020998, etc. It is also possible to use the oxime ester-based photopolymerization initiator described above.

<Organic solvent (D)>

The photosensitive coloring composition of the present invention contains an organic solvent (D). With the organic solvent (D), the colorant is sufficiently dispersed and permeated into the colorant carrier, and the filter segment can be easily formed by coating the dry film thickness on a substrate such as a glass substrate to a dry film thickness of 0.2 to 5 μm.

An organic solvent can be used individually by 1 type or in mixture of 2 or more types. In addition, since the solvent can adjust the coloring composition to an appropriate viscosity and form a filter segment having a target uniform film thickness, based on the total weight of the colorant (100% by mass), 500 to 4000% by mass It is preferable to use it in quantity.

The organic solvent (D) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3- Butylene glycol diacetate, 1,4-butanediol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene- 1-one, 3, 3, 5-trimethylcyclohexanone, 3-ethoxyethylpropionate, 3-methyl-1, 3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy- 3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N -Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chloro Toluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, Ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl Ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, Diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene Glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, Propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

These solvents can be used individually or in combination of 2 or more types.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, ethylene glycol monomethyl ether acetate, because of the good dispersibility and penetrability of the colorant and the applicability of the photosensitive composition, Acetates such as ethylene glycol monoethyl ether acetate, 1,3-butylene glycol diacetate, cyclohexanol acetate, 1,4-butanediol diacetate, butanediol diacetate, benzyl alcohol, diacetone alcohol, 1-methoxy- Alcohols such as 2-propanol and 3-methoxybutanol, ketones such as cyclohexanone, and ethyl 3-ethoxypropionate are preferably used.

<Polymerizable compound (E)>

The photosensitive coloring composition of this invention contains a polymeric compound (E). The polymerizable compound (E) includes a monomer or oligomer that is cured by ultraviolet light, heat, or the like to produce a transparent resin.

Monomers and oligomers that produce transparent resins by curing with ultraviolet light or heat include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxyl Propyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol Di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, Trimethylolpropane PO modified tri(meth)acrylate, trimethylolpropane EO modified tri(meth)acrylate, isocyanuric acid EO modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate rate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, Bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tri Various acrylic acid esters and methacrylic acid esters such as cyclodecanyl (meth)acrylate, ester acrylate, (meth)acrylic acid ester of methylolated melamine, epoxy (meth)acrylate, urethane acrylate, (meth)acrylic acid, Styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, acrylonitrile, etc. Although can be mentioned, it is not necessarily limited to these.

These polymeric compounds can be used individually or in combination of 2 or more types.

As these commercial products, KAYARAD R-128H, KAYARAD R526, KAYARAD PEG400DA, KAYARAD MAND, KAYARD NPGDA, KAYARAD R-167, KAYARAD HX-220, KAYARAD R-551, KAYARAD R712, manufactured by Nippon Kayaku Co., Ltd. KAYARAD R-604, KAYARAD R-684, KAYARAD GPO-303, KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPEA-12, KAYARAD DPHA-2 C, KAYARAD D-310, KAYARAD D-330, KAYARAD DPCA-20, KAYARAD DPCA- 30, KAYARAD DPCA-60, KAYARAD DPCA-120, and M-303, M-305, M-306, M-309, M-310, M-321, M-325, M from TOAGOSEI CO., LTD. -350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408 , M-211 B, M-101 A, OSAKA ORGANIC CHEMICAL IND. LTD. Viscoat#310 HP, Viscoat#335 HP, Viscoat#700, Viscoat#295, Viscoat#330, Viscoat#360, Viscoat#GPT, Viscoat#400, Viscoat#405, Shin-Nakamura Chemical Co., Ltd. No. A-9300 etc. are mentioned.

It is preferable that content of a polymeric compound (E) with respect to all non-volatile matter is 15-45 mass %. More preferably, the content is 20 to 35% by mass. If it is less than the above, the tapered portion of the photosensitive coloring composition pattern becomes elongated, making it difficult to form a high-precision fine pixel pattern. In the case of more than the above, the inconvenience of deterioration of resolution or residue may arise.

(polymerizable compound having an acidic group)

The polymerizable compound in the present invention may contain a polymerizable compound having an acidic group. As an acidic group, a sulfonic acid group, a carboxy group, a phosphoric acid group, etc. are mentioned.

The polymerizable compound having an acidic group is, for example, an esterified product of a polyhydric alcohol and (meth)acrylic acid, poly(meth)acrylates containing a free hydroxyl group, and dicarboxylic acids; ) esters of acrylates; and the like. As a specific example, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc. Monoesters containing free carboxyl groups of hydroxyoligoacrylates or monohydroxyoligomethacrylates and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and terephthalic acid; Propane-1,2,3-tricar Boxylic acid (tricarbaryl acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene- Tricarboxylic acids such as 1, 3, 5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate Oligoester products containing free carboxy groups with monohydroxy monoacrylates or monohydroxy monomethacrylates such as the like are exemplified.

As these commercial products, OSAKA ORGANIC CHEMICAL IND. LTD. Viscoat #2500 P manufactured by TOAGOSEI CO., LTD., M-5300, M-5400, M-5700, M-510, M-520, etc. can be used suitably.

The polymeric compound which has such an acidic group can be used individually or in combination of 2 or more types.

(Polymeric compound having a urethane bond)

The polymerizable compound in the present invention may contain a polymerizable compound containing at least one ethylenically unsaturated bond and at least one urethane bond. For example, polyfunctional urethane acrylate obtained by reacting polyfunctional isocyanate with (meth)acrylate having a hydroxyl group, or polyfunctional isocyanate obtained by reacting polyfunctional isocyanate with alcohol and further reacting (meth)acrylate having a hydroxyl group. Functional urethane acrylate etc. are mentioned.

As (meth)acrylate having a hydroxyl group, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate rate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propane oxide-modified penta(meth)acrylate, Dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, epoxy group-containing compound and carboxy(meth)acryl A reaction product of a rate, a polyol polyacrylate containing a hydroxyl group, and the like are exemplified.

Moreover, as polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, etc. are mentioned.

In addition, although there is no restriction on the structure of the alcohol, when a polyhydric alcohol is used, the crosslinking degree of the cured coating film increases and the coating film resistance increases, so it is preferable. Examples of the polyhydric alcohol include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, and pentaerythritol.

As these commercial products, KYOEISHA CHEMICAL CO., Ltd. AH-600, AT-600, UA-306 H, UA-306 T, UA-306 I, UA-510 H, UF-8001 G, DAUA-167, Shin-Nakamura Chemical Co., Ltd. No. UA-160 TM, OSAKA ORGANIC CHEMICAL IND. LTD. UV-4108 F, UV-4117 F, etc. can be used conveniently.

These photopolymerizable monomers having a urethane bond can be used alone or in combination of two or more.

<binder resin>

The photosensitive coloring composition of the present invention may contain a binder resin. Specific examples of the binder resin include thermoplastic resins and thermosetting resins.

(thermoplastic resin)

The thermoplastic resin used for the binder resin is, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane type resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. Among them, it is preferable to use an acrylic resin.

(thermosetting resin)

Examples of the thermosetting resin used for the binder resin include epoxy resins, benzoguanamine resins, rosin-modified maleic resins, rosin-modified fumaric acid resins, melamine resins, urea resins, cardo resins, and phenolic resins. .

The thermosetting resin may be, for example, an epoxy compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, a cardo compound, and a low molecular weight compound of a phenol compound. It is not limited to this. By including such a thermosetting resin, the resin reacts during firing of the filter segment, increases the crosslinking density of the coating film, improves heat resistance, and suppresses pigment aggregation during firing of the filter segment. Among these, an epoxy resin, a cardo resin, or a melamine resin is preferable.

When producing a color filter using a photosensitive coloring composition, it is preferable that the binder resin is a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the visible light region of 400 to 700 nm full wave region. .

In addition, the weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to preferably disperse the colorant. In addition, the number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw/Mn is preferably 10 or less.

Since the binder resin has good film formability and various resistances, it is preferable to use it in an amount of 10 parts by mass or more in the non-volatile matter of the resin with respect to 100 parts by mass of the total colorant, and the colorant concentration is high and good color characteristics can be expressed. Therefore, it is preferable to use it in an amount of 500 parts by mass or less in the resin non-volatile matter.

In one embodiment, when the coloring composition is used in the form of an alkali-developable colored resist material, it is preferable to use an alkali-soluble vinyl-based resin prepared using an acidic group-containing ethylenically unsaturated monomer as a binder resin from the viewpoint of developability. In another embodiment, a photosensitive coloring composition may be formed for the purpose of improving photosensitivity and improving solvent resistance. In this case, an activated energy ray-curable resin having an ethylenically unsaturated double bond may be used as the binder resin. Hereinafter, these embodiments will be described in more detail.

Examples of the vinyl-based alkali-soluble resin that can be suitably used as a binder include homopolymers or copolymers prepared using an ethylenically unsaturated monomer having an acidic group such as a carboxy group, a hydroxyl group, or a sulfone group. Specific examples of the vinyl-based alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin/(anhydrous) maleic acid copolymer, a styrene/styrenesulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or an isobutylene/( Anhydrous) Maleic acid copolymer etc. are mentioned. Especially, at least 1 sort(s) of resin chosen from the (meth)acrylic resin which has an acidic group, and a styrene/styrene sulfonic acid copolymer is preferable. In particular, a (meth)acrylic resin having an acidic group is preferably used because of its high heat resistance and high transparency.

As the acidic group in the acidic group-containing ethylenically unsaturated monomer used to prepare the resin, it is preferable to have a carboxylic acid or a hydroxyl group. Examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Examples of ethylenically unsaturated monomers having a hydroxy group include, for example, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol mono( meth)acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate, or caprolactone adducts of these monomers (the number of added moles is preferably 1 to 5); and the like. .

In the case of constituting the photosensitive coloring composition for color filters as one embodiment, from the viewpoints of pigment dispersibility, penetrability, developability, and heat resistance, the binder resin is a colorant with a carboxy group acting as a colorant adsorber and an alkali-soluble group during development and a colorant. The balance between the aliphatic group and the aromatic group acting as an affinity group for the carrier and the solvent is the weight. In one embodiment, it is preferable to use a resin having an acid value of 20 to 300 mgKOH/g as a binder resin from the viewpoint of pigment dispersibility, penetrability, developability, and durability. By using a resin having an acid value within the above range, appropriate solubility in a developing solution is obtained and it is easy to form a fine pattern.

From the viewpoint of the above, it is preferable that the vinyl-based alkali-soluble resin obtained by polymerization of the acidic group-containing ethylenically unsaturated monomer has an acid value of 20 to 300 mgKOH/g and a weight average molecular weight (Mw) of 10000 to 80000. In one embodiment, the resin is good as a copolymer of methacrylic acid and other monomers such as 2-hydroxyethyl (meth)acrylate and n-butyl methacrylate.

As another embodiment, when the photosensitive coloring composition is constituted as an alkali-developable color resist for color filters, it is preferable to use an activated energy ray-curable resin having an ethylenically unsaturated double bond as a binder resin, and in particular, an ethylenically unsaturated side chain It is preferable to use an activated energy ray-curable resin having a double bond. When the resin having an ethylenically unsaturated double bond in the side chain is used as the binder resin, there is no occurrence of foreign matter in the coating film after applying the resist, and the stability of the colorant in the resist material tends to be improved. When the straight-chain resin having no ethylenically unsaturated double bond in the side chain is used, in a liquid in which the resin and the colorant are mixed, the colorant is difficult to be trapped in the resin and has a degree of freedom, so that the colorant component does not aggregate and precipitate. easy. In contrast, when an activated energy ray-curable resin having an ethylenically unsaturated double bond in the side chain is used, the colorant is easily trapped in the resin in a liquid in which the resin and the colorant are mixed. Therefore, in the solvent resistance test, it is difficult to elute the pigment, and the aggregation and precipitation of the colorant component become difficult. It is also estimated that when a film is formed by exposure to activated energy rays, the colorant molecules are fixed by three-dimensional crosslinking of the resin, and even if the solvent is removed in the subsequent development step, it is difficult for the colorant component to aggregate and precipitate.

Examples of the activated energy ray-curable resin having an ethylenically unsaturated double bond include a resin in which an unsaturated ethylenic double bond is introduced by the method (a) or (b) shown below.

[Method (a)]

Method (a) is, for example, an addition reaction of adding a carboxyl group of an unsaturated monobasic acid having an unsaturated ethylenic double bond to a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and at least one other monomer. In addition, there is a method of introducing an unsaturated ethylenic double bond and a carboxyl group by reacting a polybasic acid anhydride with the generated hydroxyl group.

The unsaturated ethylenic monomer having an epoxy group is, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate are mentioned, and even if these are used independently, even if they use two or more types together, they are not cared about. From the viewpoint of reactivity with an unsaturated monobasic acid in the next step, glycidyl (meth)acrylate is preferred.

As the unsaturated monobasic acid, (meth)acrylic acid, crotonic acid, o-, m-, p-vinyl benzoic acid, α-position haloalkyl of (meth)acrylic acid, alkoxyl, halogen, nitro, monocarboxylic acid such as cyano-substituted products An acid etc. are mentioned, Even if these are used individually or in combination of 2 or more types, they are not cared about.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride, and these may be used alone or in combination of two or more. Hydrolyzing the remaining anhydride groups by using tricarboxylic acid anhydrides such as trimellitic anhydride or using tetracarboxylic dianhydride such as pyromellitic dianhydride as necessary, such as increasing the number of carboxyl groups. can also do things. In addition, if tetrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be further increased.

As a method similar to method (a), for example, an unsaturated ethylenic monomer having an epoxy group is added to a part of the side chain carboxyl group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxy group with one or more other monomers. There is a method of introducing an unsaturated ethylenic double bond and a carboxyl group by using

[Method (b)]

As the method (b), an unsaturated ethylenic monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxy group or an unsaturated ethylenic monomer having an isocyanate group in the side chain hydroxyl group of a copolymer obtained by copolymerizing other monomers There is a method for reacting isocyanate groups.

As the unsaturated ethylenic monomer having a hydroxyl group, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate , glycerol (meth)acrylate, or hydroxyalkyl (meth)acrylates such as cyclohexanedimethanol mono(meth)acrylate, and these may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to the hydroxyalkyl (meth)acrylate, (poly)γ-valerolactone, ( (Poly) ester mono(meth)acrylates obtained by adding poly)ε-caprolactone and/or (poly) 12-hydroxystearic acid can also be used. From the viewpoint of suppressing foreign matter in the coating film, 2-hydroxyethyl (meth)acrylate or glycerol (meth)acrylate is preferred.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, but are not limited thereto. , two or more types may be used in combination.

<sensitizer>

A sensitizer can be contained in the photosensitive composition of this invention.

Examples of the sensitizer include unsaturated ketones represented by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives represented by benzyl and comparquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. Polymethine pigments, such as xanthene derivatives, thioxanthene derivatives, xanthon derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives , thiazine derivatives, oxazine derivatives, indoline derivatives, azurene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triaryl methane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazino porphyrazine derivatives , phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporpyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrillium derivatives, tetrapyrin derivatives, anurene derivatives, spiropyran derivatives, spiro oxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or mihiraketone derivatives, α-acyloxy esters, acyl phosphine oxides, methylphenylglyoxylates, benzyl, 9, 10-phenanthrene quinones, compar-quinones , ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino ) benzophenone and the like.

Further, specific examples include Makoto Okawara et al., "Color Handbook" (1986, KODANSHA ), Makoto Okawara et al., "Chemistry of Functional Pigments" (1981, CMC), Chuzaburo Ikemori et al. , "Special Functional Materials" (CMC, 1986) include, but are not limited to, sensitizers described in these. In addition, a sensitizer showing absorption with respect to light covering the ultraviolet to near-infrared range may be contained.

Among the sensitizers, examples of sensitizers that can be sensitized particularly suitably include thioxanthone derivatives, mihiraketone derivatives, and carbazole derivatives. More specifically, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 1-chloro -4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethyl carbazole, 3-benzoyl-N-ethyl carbazole, 3,6-dibenzoyl-N-ethyl carbazole, etc. are mentioned. As a commercial item, "KAYACURE DETX-S" (2,3-diethyl thioxanthone manufactured by Nippon Kayaku Co., Ltd.), "EAB-F" (4,4'-bis (diethylamino) benzophenone Hodogaya Chemical Co., Ltd.) etc. are mentioned.

These sensitizers can be used individually or in combination of 2 or more types.

Specifically, Makoto Okawara et al. "Color Handbook" (1986, KODANSHA ), Makoto Okawara et al. "Chemistry of Functional Dyes" (1981, CMC), Ikemori Chuzaburo et al. "Special Functional materials" (1986, CMC), although the sensitizers described can be mentioned, it is not limited to these. In addition, a sensitizer showing absorption with respect to light covering the ultraviolet to near-infrared range may be contained.

The content of the sensitizer is preferably 3 to 60 parts by mass, based on 100 parts by mass of the photoradical polymerization initiator contained in the coloring composition, and more preferably 5 to 50 parts by mass from the viewpoint of photocurability and developability.

<Epoxy compound>

The photosensitive composition of the present invention may contain an epoxy compound. As the epoxy compound used, a known compound having an epoxy group can be used without particular limitation.

As the epoxy compound, phenol novolak type epoxy resin, cresol novolak type epoxy resin, trishydroxyphenyl methane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenol type epoxy resins, bisphenol A novolak type epoxy resins, naphthalene backbone-containing epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, and the like.

Among these, it is preferable that the epoxy compound is an alicyclic epoxy resin from the viewpoint of improvement of water stain or heat resistance or chemical resistance.

Specific examples of the phenol novolak type epoxy resin include, for example, DIC Corporation's EPICLON N-740, EPICLON N-770, EPICLON N-775, Dow Chemical Company's D.E.N438, and Nippon Kayaku Co.,Ltd. RE-306 manufactured by Mitsubishi Chemical Corporation, jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and the like.

Specific examples of the cresol novolak type epoxy resin include DIC Corporation's EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-695, EPICLON N-665-EXP, EPICLON N-672-EXP, Nippon Kayaku Co.,Ltd. EOCN-102 S, EOCN-103 S, EOCN-104 S, UVR-6650 from Union Carbide Corporation, Sumitomo Chemical Company, Ltd. ESCN-195 and the like.

As a specific example of the trishydroxyphenyl methane type epoxy resin, Nippon Kayaku Co., Ltd. EPPN-503, EPPN-502H, EPPN-501H, Dow Chemical Company's TACTIX-742, Mitsubishi Chemical Corporation's jER E1032H60, etc. are mentioned.

As a specific example of the dicyclopentadiene phenol type epoxy resin, EPICLON EXA-7200 by DIC Corporation, TACTIX-556 by Dow Chemical Company, etc. are mentioned.

Specific examples of the bisphenol type epoxy resin include jER828 and jER1001 manufactured by Mitsubishi Chemical Corporation, UVR-6410 manufactured by Union Carbide Corporation, D.E.R-331 manufactured by Dow Chemical Company, and Nippon Steel Epoxy Manufacturing Co., Ltd. Bisphenol A type epoxy resins such as YD-8125 manufactured by Union Carbide Corporation, UVR-6490 manufactured by Nippon Steel Epoxy Manufacturing Co., Ltd. and bisphenol F-type epoxy resins such as YDF-8170.

As a specific example of the biphenol type epoxy resin, Nippon Kayaku Co., Ltd. biphenol type epoxy resins such as NC-3000 and NC-3000 H, and bixylenol type epoxy resins such as jER YX-4000 and jER YL-6121 manufactured by Mitsubishi Chemical Corporation.

As a specific example of the bisphenol A novolak-type epoxy resin, DIC Corporation EPICLON N-880, Mitsubishi Chemical Corporation jER E157S75, etc. are mentioned.

As a specific example of the naphthalene backbone-containing epoxy resin, Nippon Kayaku Co., Ltd. NC-7000, NC-7300, DIC Corporation EXA-4750, etc. are mentioned.

Specific examples of the alicyclic epoxy resin include CELLOXIDE 2021 P, 2081, 2000, EPOLEAD PB3600, PB4700, GT401, EHPE-3150, and CYCLOMER M100 manufactured by Daicel Corporation.

As a specific example of the heterocyclic epoxy resin, Nissan Chemical Industries, Ltd. Examples include TEPIC-L, TEPIC-H, and TEPIC-S.

These epoxy compounds can be used alone or in combination of two or more.

The content of the epoxy compound used in the photosensitive coloring composition of the present invention is usually 0.5 to 50% by mass, preferably 1 to 40% by mass, based on 100% by mass of the non-volatile matter of the coloring composition. When the content of the epoxy compound is within the above range, it is preferable because heat resistance is high and an excellent coating film can be obtained.

<Oxetane compound>

An oxetane compound can be added to the photosensitive composition of the present invention. As the oxetane compound, a known compound having an oxetane group can be used without particular limitation. Examples of the oxetane compound include a monofunctional oxetane group, a bifunctional oxetane group, and a bifunctional or more functional oxetane group.

Examples of monofunctional oxetane groups include (3-ethyloxetane 3-yl) methyl acrylate, (3-ethyloxetan-3-yl) methyl methacrylate, and 3-ethyl-3-hydroxymethyl oxetane. , 3-ethyl-3-(2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-(phenoxymethyl) oxetane, 3-ethyl-3-(2-methacryloxymethyl) oxetane, 3 -Ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane etc. are mentioned. As a specific example, OSAKA ORGANIC CHEMICAL IND. LTD. No. OXE-10, OXE-30, TOAGOSEI CO., LTD. OXT-101, 212, etc. are mentioned.

As a bifunctional oxetane group, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl), 1,4-bis [(3-ethyl-3-oxeta yl) methoxymethyl] benzene, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di[1-ethyl (3-oxetanyl)] methyl ether, di [1-ethyl (3-oxetanyl)] methyl ether-3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3,7-bis(3-oxetanyl)-5-oxanonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3 -oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis( 3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy) hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene Oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A Bis(3-ethyl-3-oxetanylmethyl) ether, PO modified hydrogenated bisphenol A Bis(3-ethyl-3-oxetanylmethyl) ether, EO modified bisphenol F(3-ethyl-3-oxeta Nylmethyl) ether, etc. are mentioned. As a specific example, UBE INDUSTRIES, LTD. OXBP, OXTP, TOAGOSEI CO., LTD. OXT-121, OXT-221 and the like.

Examples of the oxetane group having a bifunctional or higher group include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, and dipentaerythritol hexa(3-oxetanylmethyl) ether. -Ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, Caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, a resin containing an oxetane group (for example, an oxetane-modified phenol novolak resin described in Japanese Patent No. 3783462, etc.) or the above-mentioned OXE-30 ( and polymers obtained by radical polymerization of meth)acrylic monomers. Such a polymer can be obtained using a known polymerization method.

The content of the oxetane compound used in the photosensitive composition of the present invention is usually 0.5 to 50% by mass, preferably 1 to 40% by mass, based on 100% by mass of the non-volatile matter of the coloring composition. When the content of the oxetane compound is within the above range, it is preferable because an excellent coating film having good water staining and high chemical resistance can be obtained.

<Thiol chain transfer agent>

The photosensitive composition of the present invention may contain a thiol chain transfer agent as a chain transfer agent. By using a thiol together with a photopolymerization initiator, in the course of radical polymerization after light irradiation, thiol radicals that act as chain transfer agents and are less susceptible to polymerization inhibition by oxygen are generated, so that the obtained coloring composition is highly sensitive.

Further, polyfunctional aliphatic thiols in which two or more SH groups are bonded to aliphatic groups such as methylene and ethylene groups are preferred. More preferably, it is a polyfunctional aliphatic thiol having 4 or more SH groups. By increasing the number of functional groups, the polymerization initiation function is improved, and it is possible to cure from the surface of the pattern to the vicinity of the base material.

Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropionate. Cionate, Trimethylolpropane trithioglycolate, Trimethylolpropane trithiopropionate, Trimethylolpropane tris(3-mercaptobutyrate), Pentaerythritol tetrakithioglycolate, Pentaerythritol tetrakithiopropionate nate, trimercaptopropionic acid tris(2-hydroxyethyl) isocyanurate, 1,4-dimethyl mercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N- Dibutylamino) -4, 6-dimercapto-s-triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane trithiopropionate, pentaerythritol tetrakithiopionate A cionate is mentioned.

These thiol chain transfer agents can be used individually by 1 type or in mixture of 2 or more types.

The content of the thiol-based chain transfer agent is preferably 1 to 10%, more preferably 2.0 to 8.0% of the total non-volatile matter of the coloring composition. Within this range, the effect of the chain transfer agent increases, and the sensitivity, taper shape, wrinkles, film shrinkage, and the like become good.

<Ultraviolet rays absorber>

The photosensitive composition of the present invention may contain a UV absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and includes benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, cyanoacrylate organic compounds, and salicylate-based organic compounds. can be heard

The content of the ultraviolet absorber is preferably 5 to 70% by mass based on 100% by mass in total of the photopolymerization initiator and the ultraviolet absorber. When the content of the ultraviolet absorber is less than the above, the effect of the ultraviolet absorber is small and the resolution cannot be secured, and when the content is higher than the above, the sensitivity is lowered and pixel peeling or hole diameter becomes larger than the designed value. there is

At this time, when the photosensitive coloring composition contains a sensitizer, content of a sensitizer shall be included in content of a photoinitiator.

Moreover, as for the total content of a photoinitiator and a ultraviolet absorber, 1-20 mass % is preferable in 100 mass % of the non-volatile matter of the photosensitive coloring composition. When the total content of the photopolymerization initiator and the ultraviolet absorber is less than the above, adhesion is weakened and pixel peeling occurs, and when it is more than the above, the sensitivity is too high and the resolution may deteriorate.

At this time, when the photosensitive composition contains a sensitizer, content of a sensitizer is included in content of a photoinitiator.

Examples of benzotriazole-based organic compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, and octyl-3[3- tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate with 2-ethylhexyl-3-[3-tert-butyl-4-hydride Mixture of hydroxy-5-(5-chloro-2 H-benzotriazol-2-yl)phenyl]propionate, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl ]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2- hydroxyphenyl) benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzene propanoic acid, Compounds of 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 branched and straight chain alkyl esters, 2-(2H-benzotriazole-2- yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-( 1, 1, 3, 3-tetramethylbutyl) phenol.

Specifically, "TINUVIN P", "TINUVIN PS", "TINUVIN 109", "TINUVIN 234", "TINUVIN 326", "TINUVIN 328", "TINUVIN 329", "TINUVIN 360", "TINUVIN" manufactured by BASF. 384-2", "TINUVIN 900", "TINUVIN 928", "TINUVIN 99-2", "TINUVIN 1130", "ADEKSTAB LA-29" manufactured by ADEKA, Otsuka Chemical Co., Ltd. The first "RUNA-93" etc. are mentioned.

As the triazine-based organic compound, 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2[4,6-bis( 2,4dimethylphenyl)1,3,5triazine2yl]5[3(dodecyloxy)2hydroxypropoxy]phenol, 2-(2,4-dihydroxyphenyl)-4,6-bis (2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl-glycidic acid ester reaction product, 2,4-bis "2-hydroxy-4-butoxyphenyl" -6 -(2,4-dibutoxyphenyl)-1,3-5-triazine etc. are mentioned.

More specifically, CHEMIPRO KASEI KAISHA, LTD. "KEMISORB 102" manufactured by BASF, "TINUVIN 400", "TINUVIN 405", "TINUVIN 460", "TINUVIN 477-DW", "TINUVIN 479", "TINUVIN 1577", "ADEKASTAB LA-46" manufactured by ADEKA , "ADEKASTAB LA-F70", and "CYASORB UV-1164" manufactured by SUNCHEMICAL CO., LTD.

Examples of the benzophenone organic compound include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2-hydroxyl. -4-n-octoxy benzophenone, 2,2-di-hydroxy-4-methoxy benzophenone, etc. are mentioned.

More specifically, CHEMIPRO KASEI KAISHA, LTD. "KEMISORB 10", "KEMISORB 11", "KEMISORB 11S", "KEMISORB 12", "KEMISORB 111", SHIPRO KASEI KAISHA, LTD. "SEESORB 101", "SEESORB 107" manufactured by ADEKA, "ADEKASTAB 1413" manufactured by ADEKA, etc. are mentioned.

<Polymerization inhibitor>

The photosensitive composition of the present invention may contain a polymerization inhibitor in order to prevent photosensitization due to diffracted light of a mask during exposure. By adding a polymerization inhibitor, an effect of preventing curing from advancing to the outside of a desired pattern by chain polymerization by photosensitization is obtained.

Examples of polymerization inhibitors include catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4- Ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert- Alkyl catechol compounds such as butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, 3,5-di-tert-butyl catechol, 2-methyl resorcinol, 4-methyl resorcy Nol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, 2-n-butyl resorcinol, 4-n-butyl resorcinol, 2- Alkyl resorcinol compounds such as tert-butyl resorcinol and 4-tert-butyl resorcinol, alkyls such as methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, tert-butyl hydroquinone, and 2,5-di-tert-butyl hydroquinone Phosphine compounds such as hydroquinone compounds, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine and tribenzylphosphine, trioctylphosphine oxide and triphenylphosphine oxide oxide compounds, phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite, pyrogallol, fluoroglucin, and the like. The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass with respect to 100 parts by mass of the coloring composition excluding the solvent. Within this range, the effect of the polymerization inhibitor increases, and the linearity of the taper, the wrinkles of the coating film, the pattern resolution, and the like become good.

<Antioxidant>

The photosensitive composition of the present invention may contain an antioxidant. Antioxidants can increase the transmittance of the coating film (to prevent the photopolymerization initiator or thermosetting compound included in the red photosensitive composition from being oxidized and yellowed by thermal curing or the thermal process of ITO annealing. In particular, the coloring composition When the colorant concentration is high, the amount of crosslinking component in the coating film decreases, so the use of a highly sensitive crosslinking component or the increase in the amount of the photopolymerization initiator increases the yellowing of the heat process.

Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

The "antioxidant" in the present invention may be any compound having an ultraviolet absorbing function, a radical replenishment function, or a peroxide decomposition function. benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. In addition, it is preferable that the antioxidant used in the present invention does not contain a halogen atom.

Among these antioxidants, preferred are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants from the viewpoint of coexistence of transmittance and sensitivity of the coating film.

As the hindered phenolic antioxidant, 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl) , 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3 , 5-di-t-butyl anilino) -1,3,5-triazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2 , 6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 4,4'-butylidene-bis-(2-t -butyl-5-methylphenol), 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'-thiodi Ethylbis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t- Butylphenyl)-butane, 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol , N,N-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), and the like. In addition, oligomer type and polymer type compounds having a hindered phenol structure may also be used. Specific examples include ADEKASTAB AO-20, AO-30, AO-40, AO50, AO60, AO80, AO320 manufactured by ADEKA Corporation, CHEMIPRO KASEI KAISHA, LTD. KEMINOX101, 179, 76, 9425, IRGANOX1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425 WL, 1520 L, 245, 259, 3114, 5057, 565, SUNCHEMICAL CO manufactured by BASF Co., Ltd. .,LTD. Cyanox CY-1790, CY-2777 and the like.

As the hindered amine antioxidant, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-p peridyl) sebacate, N, N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2, 6, 6-tetramethyl-4-piperidyl) amino-N- (2, 2, 6, 6-tetramethyl-4-piperidyl) propionamide, tetrakis (2, 2, 6, 6-tetra Methyl-4-piperidyl)(1,2,3,4-butanetetracarboxylate, poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-tri Azine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethyl{(2,2,6,6-tetramethyl-4-piperidyl) ) imino}], poly[(6-morpholino-1,3,5-triazine-2,4-diyl){(2,2,6,6-tetramethyl-4-piperidyl)imino ｝hexamethine｛(2,2,6,6-tetramethyl-4-piperidyl)imino｝】, dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6 , polycondensate with 6-tetramethylpiperidine, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl -4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other hindered amine structures It is also possible to use oligomer type and polymer type compounds etc. As specific examples, ADEKASTAB LA-52, LA-57, LA-63 P, LA-68, LA-72, LA-77 Y, LA-77 G manufactured by ADEKA Co., Ltd. , LA-81, LA-82, LA-87, LA-402 F, LA-502 XP, CHEMIPRO KASEI KAISHA, LTD. KAMISTAB29, 62, 77, 29, 94, BASF Corporation TinuVin249, TINUVIN111FDL, 123, 144 , 292, 5100, CYASORB UV-3346, UV-3529, UV-3853 manufactured by SUNCHEMICAL CO., LTD.

As the phosphorus antioxidant, tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, di Phenylisodecyl phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris(nonylphenyl) phosphite, 4,4'isopropylidenediphenolalkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl Phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(biphenyl) phosphite, distearylpentaerythritol diphosphite, di(2,4-di-t-butylphenyl) pentaerythritol Diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatri Decyl 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester , sodium bis(4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyl oxy)-benzene, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like. In addition, oligomer type and polymer type compounds having a phosphite structure may also be used. Specific examples include ADEKASTAB PEP-36, PEP-8, HP-10 manufactured by ADEKA Corporation, ADEKASTAB 2112, 1178, 1500, C, 3013, TPP manufactured by ADEKA Corporation, IRGAFOS168 manufactured by BASF Corporation, and clariant chemicals ltd. HostanoxP-EPQ and the like.

As the sulfur-based antioxidant, 2,2-thio-diethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis[(octylthio)methyl ]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol,2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1 , 3-diylbis [3- (dodecylthio) propionate], 2, 2-thio-diethylene bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] and the like. In addition, oligomer type and polymer type compounds having a thioether structure may also be used.

As a specific example, ADEKASTAB AO-412S by ADEKA Corporation, AO-503, CHEMIPRO KASEI KAISHA, LTD. KEMINOXPLS and the like.

As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure and the like can be used.

Specific examples include ADEKASTAB LA-29, LA-31 RG, LA-32, LA-36, and -412 S manufactured by ADEKA Corporation, CHEMIPRO KASEI KAISHA, LTD. Examples include KEMISORB71, 73, 74, 79, 279, TINUVIN PS, 99-2, 384-2, 900, 928, and 1130 manufactured by BASF Corporation.

Examples of benzophenone antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and 4-dodecyloxy-2. -Hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzo Phenone, 2,2', 4,4'-tetrahydroxy benzophenone, 2-hydroxy-4-methoxy-5 sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc. can be heard In addition, oligomer type and polymer type compounds having a benzophenone structure may also be used. As a specific example, ADEKASTAB 1413 by ADEKA Corporation, CHEMIPRO KASEI KAISHA, LTD. No. KEMISORB10, 11, 11 S, 12, 111, SUNCHEMICAL CO.,LTD. Examples include UV-12 and UV-329.

Examples of the triazine antioxidant include 2,4-bis(allyl)-6-(2-hydroxyphenyl)1,3,5-triazine and the like. In addition, oligomer type and polymer type compounds having a triazine structure may also be used. As a specific example, ADEKASTAB LA-46, F70 by ADEKA Corporation, CHEMIPRO KASEI KAISHA, LTD. KEMISORB102 manufactured by BASF Co., Ltd. TINUVIN400, 405, 460, 477, 479, SUNCHEMICAL CO., LTD. CYASORB UV-1164 etc. are mentioned.

Examples of salicylic acid ester antioxidants include phenyl salicylate, p-octylphenyl salicylate, and p-tert butylphenyl salicylate. In addition, oligomer type and polymer type compounds having a salicylic acid ester structure may also be used.

These antioxidants can be used alone or in combination of two or more.

In addition, the content of the antioxidant is more preferable in the case of 0.5 to 5.0 mass% in 100 mass% of the non-volatile matter of the coloring composition, because the transmittance, spectral characteristics, and sensitivity are good.

<Adhesion improver>

The photosensitive composition of the present invention may contain an adhesion improving agent such as a silane coupling agent in order to increase adhesion to a substrate. By improving the adhesion by the adhesion improving agent, the reproducibility of thin wires is improved and the resolution is improved.

Examples of adhesion improving agents include vinylsilanes such as vinyl trimethoxysilane and vinyl triethoxysilane, 3-methacryloxypropylmethyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, and 3-methacryloxypropylmethyl. (meth)acrylic silanes such as diethoxysilane, 3-methacryloxypropyl triethoxysilane, and 3-acryloxypropyl trimethoxysilane 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3 -Epoxysilanes such as glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N- 2-(aminoethyl)-3-aminopropylmethyl dimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxy Silane, 3-triethoxysilyl-N-(1, 3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyl trimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3 -Aminosilanes such as the hydrochloride of aminopropyl trimethoxysilane, mercaptos such as 3-mercaptopropylmethyl dimethoxysilane and 3-mercaptopropyl trimethoxysilane, p-styryl trimethoxysilane, etc. Styryls, ureides such as 3-ureidopropyl triethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide, and isocyanates such as 3-isocyanate propyltriethoxysilane Silane couples A ring agent can be mentioned. The adhesion improving agent can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the coloring agent in the coloring composition. It is more preferable because the effect becomes large within this range and the balance of adhesiveness, resolution, and sensitivity is good.

<leveling agent>

It is preferable to add a leveling agent to the photosensitive composition of this invention for the purpose of improving the coating property of the composition on a transparent substrate, and the drying property of a colored film. As the leveling agent, various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic (surfactants, anionic surfactants) can be used.

Examples of the silicone surfactant include straight-chain polymers having siloxane bonds and modified siloxane polymers having organic groups introduced into side chains or terminals.

As a specific example, BYK-Chemie Inc. No. BYK-300, BYK-306, BYK-310, BYK-313, BYK-315 N, BYK-320, BYK-322, BYK-323, BYK-330, BYK-331, BYK-333, BYK-342, BYK-345/346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-377, BYK-378, BYK-3455, BYK-UV3510, BYK-3570; No., FZ-7001, FZ-7002, FZ-2110, FZ-2122, FZ-2123, FZ-2191, FZ-5609, Shin-Etsu Chemical Co., Ltd. No. X-22-4952, X-22-4272, X-22-6266, KF-351 A, K354L, KF-355 A, KF-945, KF-640, KF-642, KF-643, X-22 -6191, X-22-4515, KF-6004, etc. are mentioned.

As a fluorochemical surfactant, surfactant which has a full fluorocarbon chain is mentioned.

As a specific example, AGC SEIMI CHEMICAL CO., LTD. Surflon S-242, S-243, S-420, S-611, S-651, S-386, DIC Corporation MEGAFACE F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS-21, Sumitomo 3M Limited FC-4430, FC- 4432, Mitsubishi Materials Electronic Chemicals Co., Ltd. No. EF-PP31N09, EF-PP33G1, EF-PP32C1, NEOS COMPANY LIMITED Futagent 602 A, etc. are mentioned.

As nonionic surfactants, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristel ether, polyoxyethylene Octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene alkenyl ether, polyoxyethylene nonylphenyl ether , polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate , sorbitan monolaurate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, Polyoxyethylene Sorbitan Monooleate, Polyoxyethylene Sorbitan Triisostearate, Polyoxyethylene Sorbit Tetraoleate, Glycerol Monostearate, Glycerol Monooleate, Polyethylene Glycol Monolaurate, Polyethylene Glycol Monostearate, Polyethylene and alkylbetaines such as glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylenealkylamine, alkylalkanolamide, alkylimidazoline, and alkyldimethylaminoacetic acid betaine. .

Specific examples include Kao Corporation's EMULGEN 103, EMULGEN 104 P, EMULGEN 106, EMULGEN 108, EMULGEN 109 P, EMULGEN 120, EMULGEN 123 P, EMULGEN 130 K, EMULGEN 147, EMULGEN 150, EMULGEN 210 P , EMULGEN 220, EMULGEN 306 P , EMULGEN 320 P, EMULGEN 350, EMULGEN 404, EMULGEN 408, EMULGEN 409 PV, EMULGEN 420, EMULGEN 430, EMULGEN 705, EMULGEN 707, EMULGEN 709, EMULGEN 1108, EMULGEN 1 118 S-70, EMULGEN 1135 S-70, EMULGEN 1150 S-60, EMULGEN 2020 G-HA, EMULGEN 2025 G, EMULGEN LS-106, EMULGEN LS-110, EMULGEN LS-114, EMULGEN MS-110, EMULGEN A-60, EMULGEN A-90, EMULGEN B-66, EMULGEN PP-290, LATEMUL PD-420, LATEMUL PD-430, LATEMUL PD-430 S, LATEMUL PD450, Rheodol SP-L10, Rheodol SP-P10, Rheodol SP-S10V, Rheodol SP-S20, Rheodol SP-S30V, Rheodol SP -O10V, Rheodol SP-O30V, Rheodol super SP-L1, Rheodol AS-10 V, Rheodol AO-10 V, Rheodol AO-15 V, Rheodol TW-L120, Rheodol TW-L106, Rheodol TW-P120, Rheodol TW- S120V, Rheodol TW-L106V, Rheodol TW-S320V, Rheodol TW-O120V, Rheodol TW-O106V, Rheodol TW-IS399C, Rheodol super TW-L120, Rheodol 430 V, Rheodol 440 V, Rheodol 460 V, Rheodol MS-50, Rheodol MS-60, Rheodol MO-60, Rheodol MS-165 V, EMANON 1112, EMANON 3199 V, EMANON 3299 V, EMANON 3299 RV, EMANON 4110, EMANON CH-25, EMANON CH-40, EMANON CH-60(K ), AMIET 102, AMIET 105, AMIET 105 A, AMIET 302, AMIET 320, Aminon PK-02 S, Aminon L-02, HOMOGENOL L-95, Adeka Pluronic L-23, 31, 44, 61, manufactured by ADEKA Co., Ltd. 62, 64, 71, 72, 101, 121, Adeka Pluronic TR-701, 702, 704, 913 R and the like.

Cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, and cetyl trimethyl ammonium chloride, and ethylene oxide adducts thereof.

As specific examples, Kao Corporation ACETAMIN 24, 26, QUARTAMIN 24 P, 86 P conc, Shin-Etsu Chemical Co., Ltd. No. KP341, KYOEISHA CHEMICAL CO.,Ltd. and (meth)acrylic acid-based (co)polymers Polyflow No.75, No.90, and No.95.

As the anionic surfactant, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalinesulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate , triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of a styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate esters.

Specific examples include Futagent 100 and 150 manufactured by NEOS COMPANY LIMITED, ADEKA HOPE YES-25 manufactured by ADEKA Corporation, ADEKA COL TS-230 E, PS-440 E, and EC-8600.

Surfactant used as a leveling agent may use only 1 type, and may combine 2 or more types.

When the photosensitive composition of the present invention contains a surfactant, the added amount of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total non-volatile content of the composition of the present invention. Within this range, the balance of the applicability|paintability of a coloring composition, pattern adhesiveness, and a transmittance|permeability becomes favorable.

The photosensitive composition of this invention may contain only 1 type of surfactant, and may contain 2 or more types. When containing two or more types, it is preferable that the total amount becomes the said range.

<Amine compound>

Further, the photosensitive composition of the present invention may contain an amine compound having a function of reducing dissolved oxygen. As such an amine compound, triethanolamine, methyl dimethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-dimethyl Aminobenzoic acid 2-ethylhexyl, N, N-dimethyl para toluidine, etc. are mentioned.

<Method for producing colored dispersion>

The photosensitive coloring composition included in the present invention, a colorant, a dispersant, a colorant carrier such as a binder resin and / or a solvent, preferably together with a dispersing aid, kneader, two roll mill, three roll mill, ball mill, horizontal sand mill , It can be prepared based on a colored dispersion prepared by finely dispersing using various dispersion means such as a vertical sand mill, an annular bead mill, or an atrider. At this time, two or more kinds of colorants, etc. may be simultaneously dispersed in the colorant carrier, or separately dispersed in the colorant carrier may be mixed. When the solubility of the coloring agent such as dye is high, specifically, the solubility to the solvent used is high, and it is dissolved by stirring and in a state in which foreign matter is not confirmed, fine dispersion may not be performed. When preparing the colored dispersion in the present invention, it is preferable to disperse the colorant (A) using the resin type dispersant (B).

Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or alkali developing type coloring composition. The solvent developing type or alkali developing type coloring composition can be prepared by mixing the colorant dispersion, the photopolymerizable monomer and/or the photopolymerization initiator, and, if necessary, a solvent, other dispersing aids, and additives. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<dispersion preparation>

When the colorant is dispersed in the colorant carrier, a dispersing aid such as a pigment derivative, a resin type dispersant, or a surfactant can be contained as appropriate. Since the dispersing aid has a large effect of preventing reagglomeration of the colorant after dispersion, a colored composition obtained by dispersing the colorant in a colorant carrier using the dispersing aid has good brightness, contrast, and storage stability.

[Resin type dispersing agent]

Although the photosensitive composition of this invention contains the above-mentioned resin type dispersing agent (B), you may contain conventionally well-known resin type dispersing agents as others.

The resin type dispersant has a colorant affinity site having a property of adsorbing to the added colorant and a site compatible with the colorant carrier, and has a function of adsorbing to the added colorant and stabilizing the dispersion to the colorant carrier. Specifically as the resin type dispersant, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acids acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkylene imine) with polyester having a free carboxyl group; Oil-based dispersants such as salts thereof, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and water-soluble resins or water-soluble such as polyvinylpyrrolidone A polymer compound, a polyester type, a modified polyacrylate type, an ethylene oxide/propylene oxide addition compound, a phosphoric acid ester type, etc. are used, and these may be used alone or in combination of two or more types, but are not necessarily limited thereto.

(Basic resin type dispersant)

As the dispersing agent used in the present invention, a basic resin-type dispersing agent having a basic functional group is preferable, and a nitrogen atom-containing graft copolymer or a functional group containing a tertiary amino group, a quaternary ammonium base, or a nitrogen-containing heterocyclic ring in the side chain. , nitrogen atom-containing acrylic block copolymers and urethane-based polymer dispersants are preferred. The resin type dispersant is preferably used in an amount of about 5 to 200% by weight based on the total amount of the colorant, and more preferably in an amount of about 10 to 100% by weight from the viewpoint of film formability.

As commercially available resin type dispersants, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, manufactured by byk-chemie japan k.k. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti- Terra-U, 203, 204, or BYK-P104, P104S, 220 S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940 from Lubrizol Japan Ltd.; 16000,17000,18000,20000,21000,24000,26000,27000,28000,31845,32000,32500,32550,33500,32600,34750,35100,36 600, 38500, 41000, 41090, 53095, 55000, 56000, 76500 etc. , EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408 manufactured by BASF , 4300, 4310 , 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502 , 1503, etc., Ajinomoto Fine-Techno Co., Inc. Ajisper-PA111, PB711, PB821, PB822, PB824 and the like are preferred.

(Acidic resin type dispersing agent)

In addition, as the resin type dispersant used in the present invention, an acidic resin type dispersant can also be suitably used. As a resin type dispersant used in the present invention, it is also preferable to contain the following (S1) or (S2) as a resin type dispersant having a carboxy group.

(S1) A resin type dispersant that is a reaction product between a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of tricarboxylic acid anhydride and/or tetracarboxylic dianhydride.

(S2) A resinous dispersant that is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of tricarboxylic acid anhydride and/or tetracarboxylic dianhydride.

<<resin type dispersing agent (S1)>>

Resin type dispersing agent (S1) can be manufactured by well-known methods, such as WO2008/007776, Unexamined-Japanese-Patent No. 2008-029901, and Unexamined-Japanese-Patent No. 2009-155406. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal. For example, it can be obtained as a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) in the presence of a compound (q) having a hydroxyl group. . As the compound (q) having a hydroxyl group, a compound having a hydroxyl group and a thiol group in the molecule is preferable. Since it is preferable that there are a plurality of terminal hydroxyl groups, among them, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

That is, a more preferable example of a polymer having two hydroxyl groups at one end is an ethylenically unsaturated monomer (r1) containing a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. ) can be obtained as the polymer (p1) polymerized. While the hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of tricarboxylic acid anhydride and/or tetracarboxylic dianhydride to form an ester bond, the anhydrous ring is ring-opened to form carboxylic acid.

≪Resin type dispersing agent (S2)≫

The resin type dispersant (S2) can be prepared by known methods such as Japanese Patent Laid-Open No. 2009-155406, Japanese Patent Laid-Open No. 2010-185934, and Japanese Unexamined Patent Publication No. 2011-157416, for example, a hydroxyl group It is obtained by polymerizing the ethylenically unsaturated monomer (r) in the presence of a reaction product between the hydroxyl group of the compound (q) and the acid anhydride group of tricarboxylic acid anhydride and/or tetracarboxylic dianhydride. Among them, in the presence of a reaction product between the hydroxyl group of the compound (q1) having two hydroxyl groups and one thiol group in the molecule and an acid anhydride group of tricarboxylic acid anhydride and/or tetracarboxylic dianhydride, monomer (r1) It is preferably a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing

(S1) and (S2) are differences in whether introduction of the polymer portion obtained by polymerizing the ethylenically unsaturated monomer (r) is performed first or next. Although molecular weight and the like may differ slightly depending on various conditions, they may be theoretically the same if the material and reaction conditions are the same.

[Dye Derivative]

As the dye derivative used in the present invention, a known dye derivative having an acidic group, a basic group, a neutral group or the like in an organic dye residue can be used. For example, compounds having acidic functional groups such as sulfo groups, carboxyl groups, and phosphoric acid groups, and amine salts thereof, compounds having basic functional groups such as tertiary amino groups at terminals or sulfonamide groups, and neutral functional groups such as phenyl groups and phthalimide alkyl groups. A compound having Japanese Patent Publication No. 63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, Japanese Patent Publication No. 5-9469, Japanese Unexamined Patent Publication No. 2001-335717, Japanese Unexamined Patent Publication No. 2003-128669, Japanese Unexamined Patent Publication No. 2004-091497, Japanese Unexamined Patent Publication No. 2007-156395, Japanese Unexamined Patent Publication No. 2008-094873, Japanese Unexamined Patent Publication 2008- Publication No. 094986, Japanese Unexamined Patent Publication No. 2008-095007, Japanese Unexamined Patent Publication No. 2008-195916, Japanese Patent No. 4585781, Japanese Unexamined Patent Publication No. 2006-291194, Japanese Unexamined Patent Publication No. 2007-226161, Japanese Unexamined Patent Publication 2007 -314681, Japanese Unexamined Patent Publication 2007-314785, Japanese Unexamined Patent Publication 2012-226110, Japanese Unexamined Patent Publication 2017-165820, Japanese Unexamined Patent Publication 2005-181383, etc. can In addition, although these documents sometimes describe a pigment derivative as a derivative, a pigment derivative, a pigment dispersant, or just a compound, etc., a compound having a functional group such as an acidic group, a basic group, or a neutral group in the organic pigment residue described above is a pigment. It is synonymous with the derivative. In addition, these can be used individually or in mixture of 2 or more types.

The content of the dye derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more with respect to 100 parts by mass of the colorant from the viewpoint of improving the dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by mass or less, more preferably 35 parts by mass or less.

By adding a pigment derivative to the pigment and carrying out a dispersion treatment such as wet dispersion using two rolls, three rolls, or beads, the pigment derivative is adsorbed on the surface of the pigment, making the surface of the pigment polar, and adsorption of the resin type dispersant is promoted. Compatibility with pigments, pigment derivatives, resinous dispersants, solvents, and other additives is improved, and dispersion stability and time-lapse viscosity stability when used as colored compositions or colored curable compositions are improved. In addition, by improving the compatibility, the stability over time of the coating film when the colored curable composition is coated on glass is excellent, and the waiting time from application of the colored curable composition to exposure (PCD: Post Coating Delay) or waiting time from exposure to heat treatment ( Stability and characteristic dependence of the pattern shape, etc., and line width sensitivity stability with respect to PED: Post Exposure Delay) become good. In addition, development time variance and development residues are also suppressed.

[Surfactants]

Examples of surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkylnaphthalinesulfonate, sodium alkyl diphenylether disulfonate, Anionic surfactants such as monoethanolamine uryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate; polyoxyethylene oleic acid; Nonionic surfactants such as ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl quaternary ammonium salts; or cationic surfactants such as ethylene oxide adducts thereof; alkyl betaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazoline. It can be, but it is not necessarily limited to these.

When adding a surfactant, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the coloring agent. When the content of the surfactant is less than 0.1 part by mass, the added effect is difficult to obtain, and when the content is more than 55 parts by mass, the dispersion may be affected by an excessive dispersant.

<Removal of coarse particles>

The colored dispersion or photosensitive composition of the present invention is obtained by means such as centrifugal separation, filtration with a sinter filter or membrane filter, coarse particles of 5 μm or more, preferably 1 μm or more coarse particles, more preferably 0.5 μm or more coarse particles and It is preferable to remove the mixed dust. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, it is desirable that it is 0.3 micrometer or less.

As a filter, if it has conventionally been used for filtration purposes etc., it can be used without particular limitation. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6, 6), polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight) and the like. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore diameter of the filter is preferably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. By setting it as this range, it becomes possible to remove fine foreign material reliably. Moreover, it is also preferable to use a fibrous filter medium. Examples of the fibrous filter medium include polypropylene fibers, nylon fibers, and glass fibers. Specifically, Roki Techno Co., Ltd. Filter cartridges of our SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) can be used.

When using filters, you may combine other filters. In that case, the filtration by the first filter may be performed only once, or may be performed twice or more.

In addition, you may combine the 1st filter of a different hole diameter within the above-mentioned range. The hole diameter here can refer to the nominal value of the filter maker. Commercially available filters are, for example, manufactured by Nihon Pall Ltd. (DFA4201NXEY, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris KK (formerly Nihon Mykrolis K.K.) or KITZ MICRO FILTER CORPORATION.

＜Color filter＞

Next, the color filter of the present invention will be described.

The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment. Further, the color filter may further include a magenta color filter segment, a cyan color filter segment, and a yellow filter segment. It is preferable that the color filter of this invention is what a red filter segment is formed from in the red photosensitive composition of this invention.

<Production method of color filter>

A color filter can be manufactured by a printing method or a photolithography method.

Formation of the filter segment by the printing method is low-cost and excellent in mass productivity as a manufacturing method of a color filter, since patterning occurs only by repeating printing and drying of a coloring composition prepared as a printing ink. In addition, with the development of printing technology, it is possible to print fine patterns with high dimensional accuracy and smoothness. In order to perform printing, it is preferable to set it as a composition which prevents ink from drying and solidifying on a printing board or a blanket. Moreover, control of the fluidity of ink on a printing press is also important, and it is also possible to adjust the ink viscosity by a dispersant or an extender pigment.

When the filter segment is formed by the photolithography method, the coloring composition prepared as the solvent developing type or alkali developing type colored resist material is coated on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating. It is applied so that the dry film thickness is 0.2 to 5 μm. Exposure (irradiation of radiation) is performed to the dried film as needed through a mask having a predetermined pattern provided in a contact or non-contact state with the film. Thereafter, after immersing in a solvent or alkali developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation can be repeated for other colors to produce a color filter. Further, in order to promote polymerization of the colored resist material, heating at 80°C to 250°C may be performed as needed. According to the photolithography method, a highly accurate color filter can be manufactured by the printing method.

When developing, aqueous solutions, such as sodium carbonate and sodium hydroxide, are used as alkaline developing solutions, and organic alkalis, such as dimethyl benzylamine and triethanolamine, can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.

Further, in order to increase exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is coated and dried to form a film preventing polymerization inhibition by oxygen, followed by exposure may be carried out.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an inkjet method, or the like other than the above methods, but the coloring composition of the present invention can be used in any method. Further, the electrodeposition method is a method for producing a color filter by electrodeposition-forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using a transparent conductive film formed on a substrate. In addition, the transfer method is a method in which filter segments are previously formed on the surface of a peelable transfer base sheet, and the filter segments are transferred to a desired substrate.

Before forming each color filter segment on a transparent substrate or a reflective substrate, a black matrix may be formed in advance. As the black matrix, a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the above-described transparent substrate or reflective substrate, and then each color filter segment may be formed. Further, on the color filter of the present invention, an overcoat film, a transparent conductive film, or the like is formed as needed.

The color filter of the present invention is bonded to a counter substrate using a sealer, injects liquid crystal from an injection hole provided in the seal part, seals the injection hole, and attaches a polarizing film or a retardation film to the outside of the substrate as necessary to display a color liquid crystal. device is manufactured. This color liquid crystal display device has twisted nematic (TN), super twisted nematic (STN), in plane switching (IPS), vertical alignment (vertical It can be used in liquid crystal display modes that perform colorization using color filters such as alignment (VA) and optical compensated bend (OCB).

In addition, the color filter of the present invention can also be used for production of color solid-state imaging devices, organic EL display devices, quantum dot display devices, electronic paper, and the like, in addition to color liquid crystal display devices.

[Example]

Below, the present invention will be specifically described by examples, but the present invention is not limited to the following examples unless the gist thereof is exceeded. In Examples and Comparative Examples, "parts" and "%" mean "parts by mass" and "% by mass".

(weight average molecular weight of resin)

The weight average molecular weight (Mw) of the resin was measured using a TSKgel column (manufactured by TOSOH CORPORATION) by GPC (manufactured by TOSOH CORPORATION, HLC-8320 GPC) equipped with an RI detector, using THF as a developing solvent, in terms of polystyrene. It is the weight average molecular weight (Mw).

(acid value of resin)

The resin acid value is a value obtained by converting the measured acid value (mgKOH/g) into non-volatile content in accordance with the potentiometric titration method of JIS 　K 0070.

<Manufacture of resin type dispersant (B)>

(Resin type dispersing agent (B-1))

8 parts of 3-mercapto-1,2-propanediol, 12 parts of pyromellitic acid anhydride, 80 parts of propylene glycol monomethyl ether acetate (PGMAc), catalyst After injecting 0.2 part of monobutyltin oxide as the mixture and substituting with nitrogen gas, the mixture was reacted at 120°C for 5 hours (first process). By measuring the acid value, it was confirmed that 95% or more of the acid anhydrides were half esterified. Next, methyl methacrylate (MMA) 30 parts, t-butylacrylate (tBA) 10 parts, ethyl acrylate (EA) 10 parts, methacrylic acid (MAA) 5 parts, benzyl methacrylate (BzMA) 10 parts part, 35 parts of 2-hydroxyethyl methacrylate (HEMA) was injected, the inside of the reaction vessel was heated to 80°C, and 1 part of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. and reacted for 12 hours (second step). It was confirmed that 95% reacted by non-volatile content measurement. Next, the inside of the flask was purged with air, 38.0 parts of 2-methacryloyloxyethyl isocyanate (MOI) and 0.1 part of hydroquinone were injected, and reaction was performed at 70°C for 4 hours (third step). After confirming the disappearance of the peak at 2270 cm -1 based on the isocyanate group by IR, the reaction solution was cooled and the non-volatile content was adjusted with PGMAc to obtain a solution of a resin type dispersant (B-1) with a non-volatile content of 40%. The acid value of the obtained resin type dispersant was 40, and the weight average molecular weight was 12,000.

(Resin type dispersing agent (B-2 to B-23))

Except for using the raw materials and injection amount described in Tables 1 and 2, the synthesis was carried out in the same manner as in the resin type dispersant (B-1), and the resin type dispersants (B-2) to (B-22) with a non-volatile content of 40% of the solution was obtained.

BTDA: 3, 3', 4, 4'-benzophenone tetracarboxylic dianhydride

MMA: methyl methacrylate

tBA: t-butyl acrylate

EA: ethyl acrylate

MAA: methacrylic acid

BzMA: Benzyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

HPMA: 2-hydroxypropyl methacrylate

FM-3: Terminal hydroxy group polycaprolactone modified methacrylate (DAICEL CHEMICAL INDUSTRIES, LTD.: PLACCEL FM-3)

MOI: 2-methacryloyloxyethyl isocyanate (made by SHOWA DENKO K.K.: Karenz MOI)

AOI: 2-acryloyloxyethyl isocyanate (manufactured by SHOWA DENKO K.K.: Karenz AOI) BEI: 1, 1-bis (acryloyloxymethyl) ethyl isocyanate (manufactured by SHOWA DENKO K.K.: Karenz BEI)

<Manufacture of binder resin>

(Acrylic resin solution 1)

Add 100 parts of propylene glycol monomethyl ether acetate to a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirring device in a separable four-neck flask, heat to 120 ° C. while injecting nitrogen gas into the vessel, and dropwise at the same temperature A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile was added dropwise through a tube over 2.5 hours to carry out a polymerization reaction.

Next, the inside of the flask was purged with air, 0.3 part of trisdimethylaminomethyl phenol and 0.3 part of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours, and the reaction was terminated when the acid value of the non-volatile matter reached 0.8, A resin solution having a weight average molecular weight of about 12,000 (measured by GPC) was obtained.

Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added and reacted at 120°C for 4 hours. Propylene glycol monomethyl ether acetate was added to prepare an acrylic resin solution 1 so that the non-volatile content was 40%.

<Manufacture of coloring agent (A)>

<Production of micronized red pigment (PR254-1)>

200 parts of diketopyrrolopyrrole red pigment C.I.Pigment Red 254 ("Irgajin RedL" 3630 manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol are injected into a stainless steel 1 gallon kneader (manufactured by INOUE MFG., INC.) and kneaded at 80°C for 6 hours. Next, this kneaded material was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight, A diketopyrrolopyrrole-based micronized red pigment (PR254-1) was obtained.

<Manufacture of micronized yellow pigment (PY139-1)>

200 parts of yellow pigment C.I. Pigment Yellow 139 ("Paliotol yellow D1819" manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were injected into a stainless steel 1 gallon kneader (manufactured by INOUE MFG., INC.) at 80°C. It was kneaded for 6 hours. Next, this kneaded material was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight, A micronized yellow pigment (PY139-1) was obtained.

<Manufacture of micronized blue pigment (PB15: 6-1))>

200 parts of phthalocyanine-based blue pigment C.I.Pigment Blue 15:6 ("LIONOL BLUE ES" manufactured by TOYOCOLOR CO., LTD., specific surface area 60 m/g), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were mixed with a stainless steel 1 gallon kneader ( INOUE MFG., Inc.), and kneaded at 80°C for 6 hours. Next, this kneaded material was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight, A phthalocyanine-based miniaturized blue pigment (PB15:6-1) was obtained.

<Manufacture of micronized purple pigment (PV23-1))>

200 parts of dioxazine-based purple pigment C.I.Pigment Violet 23 (manufactured by TOYOCOLOR CO., LTD. "LIONOGEN VIOLET RL"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were mixed with a stainless steel 1 gallon kneader (manufactured by INOUE MFG., INC.) It injected and kneaded at 80 degreeC for 6 hours. Next, this kneaded material was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight, Dioxazine-based purple micronized purple pigment (PV23-1) was obtained.

<Manufacture of micronized green pigment (PG58-1))>

200 parts of phthalocyanine-based green pigment C.I.Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were injected into a stainless steel 1 gallon kneader (manufactured by INOUE MFG., INC.), and 80 It was kneaded at °C for 6 hours. Next, this kneaded material was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight, A phthalocyanine-based micronized green pigment (PG58-1) was obtained.

<Manufacture of micronized yellow pigment (PY150-1))>

200 parts of nickel complex yellow pigment C.I. Pigment Yellow 150 (“E-4 GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were injected into a stainless steel 1 gallon kneader (manufactured by INOUE MFG., INC.) , and kneaded at 80°C for 6 hours. Next, this kneaded material was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight, A nickel complex type micronized yellow pigment (PY150-1) was obtained.

<Manufacture of micronized yellow pigment (PY185-1))>

As a yellow colorant, 200 parts of C.I. Pigment Yellow 185 (“Paliotol Yellow L 1155” by BASF), 1000 parts of sodium chloride, and 100 parts of diethylene glycol were injected into a stainless steel 1 gallon kneader (manufactured by INOUE MFG., INC.), and 100 It was kneaded at °C for 6 hours. Next, this kneaded material was put into 5 liters of warm water, stirred for 1 hour while heating at 70 ° C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C overnight. , to obtain a yellow colorant (PY185-1).

<Method for producing salt-formation compound (V)>

A salt-formation compound (V) composed of C.I.Acid Red 289 and tristearylmonomethyl ammonium chloride, which is a quaternary ammonium salt compound, was produced in the following procedure. Dissolve 10 parts of C.I.Acid Red 289 in 200 parts of water to make a 5% aqueous solution, heat to 30 to 50 ° C, and then 5.5 parts of tristearylmonomethyl ammonium to a 5% solution in methanol / water = 20/80. The chloride was dissolved and added dropwise little by little. After dripping the tristearyl monomethyl ammonium chloride solution, it stirred at 30-50 degreeC for 3 hours. After cooling to room temperature while stirring, suction filtration is performed, and after washing with water, the salt-formation compound remaining on the filter paper is removed from moisture in a dryer and dried to obtain a salt-formation compound (V) of C.I.Acid Red 289 and tristearyl monomethyl ammonium chloride. got 8 pieces

<Method for producing salt-formation compound-containing resin solution (SV)>

After stirring and mixing the following mixture so as to become uniform, it was filtered through a 5.0 μm filter to prepare a salt-formation compound-containing resin solution (SV).

Salt-formation compound (V) 　　　　　　　　　　　: 8.0 parts

Cyclohexanone: 92.0 parts

<Dye derivative>

Dye Derivative A...Compound C described in Japanese Unexamined Patent Publication No. 2007-314681

Dye derivative B...general formula 31 described in Japanese Patent Laid-Open No. 2006-291194

Dye derivative C... Compound iii described in Japanese Unexamined Patent Publication No. 2017-165820

Dye derivative D... Derivative 51 described in Japanese Patent Laid-Open No. 2005-181383

<Preparation of colored dispersion>

(Coloring composition D-1)

After stirring and mixing the following mixture so that it becomes uniform, using zirconia beads with a diameter of 0.5 mm, dispersed for 5 hours in an EIGER MILL ("Mini Model M-250 MKII" manufactured by EIGER japan CO., Ltd.), then 5.0 The colored composition (D-1) was prepared by filtering with a μm filter.

Micronized pigment (PR254-1) 　　　　　　　　 　: 13.3 parts

Dye derivative A　　　　　　　　　　　　 :0.7 part

Dye derivative B　　　　　　　　　　　　:0.7 part

Resin type dispersant (B-1) solution = 13.0 parts

Propylene glycol monomethyl ether acetate (PGMAC) 　: 72.2 parts

(Coloring composition D-2 to 65)

(Coloring compositions D-2 to 65) were prepared in the same manner as in the coloring composition D-1, except that the coloring agent, the pigment derivative, and the resinous dispersant solution were changed to the compositions shown in Tables 3 to 9.

<Production of photosensitive coloring composition for color filters>

[Examples 101-121, 201-209, 301-306 and Comparative Examples 101-104, 201-206, 301-304] (RR-1-26, RG-1-15, RB-1-10)

Each material was mixed and stirred at the formulation ratio shown in Table 10, filtered through a 1 μm filter, and photosensitive coloring compositions of each color were obtained.

Abbreviated names in Table 10 are shown below.

Photopolymerization initiator C1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (“IRGACURE 907” manufactured by BASF)

Photopolymerization initiator C2: (oxime ester system): ethane-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyl oxime ) (“IRGACURE OXE02” manufactured by BASF)

Photopolymerizable compound E1: dipentaerythritol hexaacrylate ("ARONIX" M-402" manufactured by TOAGOSEI CO., LTD.)

・Organic solvent: Propylene glycol monomethyl ether acetate

<Evaluation of photosensitive coloring composition for color filters>

About the obtained photosensitive coloring composition, it evaluated by the following method. The results are shown in Table 11.

[Viscosity and Viscosity Stability of Photosensitive Coloring Composition]

Regarding the obtained photosensitive coloring composition, TOKI SANGYO CO., LTD. The initial viscosity at 25°C was measured using a viscometer TV22. In addition, the viscosity after acceleration with passage of time at 40°C for one month was measured, and the viscosity increase rate was calculated. Evaluation was performed based on the following criteria.

◎: Initial viscosity is 10.0 Pa s or less, and viscosity increase with time is less than 40%

○: Initial viscosity is 10.0 Pa·s or less, and viscosity increase over time is 40% or more

×: the initial viscosity is 10.0 Pa·s or more;

[Pattern Formation of Filter Segments]

After coating the obtained photosensitive coloring composition on a 10 cm x 10 cm glass substrate by spin coating, it was heated at 70°C for 5 minutes in a clean oven to remove the solvent to obtain a coating film of about 2 µm. Then, after cooling this substrate to room temperature, it was exposed using an ultra-high pressure mercury lamp at an exposure amount of 50 mJ/cm 2 through a 100 μm wide (pitch 200 μm) and 25 μm wide (pitch 50 μm) stripe pattern photomask. Thereafter, the substrate was subjected to spray development using an aqueous solution of sodium carbonate at 23°C, washed with ion-exchanged water, air-dried, and heated at 230°C for 20 minutes in a clean oven. Spray development was carried out in the shortest time possible for pattern formation without developing residues on the coating film of each photosensitive coloring composition, and this was set as the appropriate development time.

The film thickness of the coating film was performed using Dektak 3030 (manufactured by Nippon Vacuum Engineering Co., Ltd.).

[Measurement of film thickness with a predetermined chromaticity]

When forming the filter segments by the above method, the number of rotations of the spin coat was appropriately changed to form a plurality of filter segments having different film thicknesses. Chromaticity was measured with a microscopic spectrophotometer ("OSP-SP100" C light source manufactured by Olympus Optical Co. Ltd.). From the measured values, in the case of a red photosensitive coloring composition, the film thickness at x = 0.655, in the case of a green photosensitive coloring composition, at y = 0.614, in the case of a blue photosensitive coloring composition, the film thickness at y = 0.049 was obtained by calculation. Evaluation was made according to the following criteria using the calculated film thickness.

◎: The film thickness is 1.2 μm or more and less than 1.8 μm

○: The film thickness is 1.8 μm or more and less than 2.2 μm

×: Film thickness is 2.2 μm or more

[Resolution evaluation]

The resolution of the pattern in the 25 μm photomask portion of the filter segment formed by the above method was visually evaluated using an optical microscope. Defective resolution means that adjacent stripe patterns are connected or defects occur. The rank of evaluation is as follows.

◎: The stripe pattern is completely independent, and no residue is visible between the lines.

○: Although the stripe pattern is completely independent, residues are visible between the lines

△: Adjacent stripe patterns are partially connected

×: Patterns of adjacent stripes are connected

[Evaluation of linearity]

The pattern in the 100 μm photomask portion of the filter segment formed by the above method was observed and evaluated using an optical microscope. The rank of evaluation is as follows. Also, C and D are levels that are difficult to use.

S: Very good linearity

A: Good linearity

B: Linearity is generally good and usable level

C: A level that partially has poor linearity and is difficult to use

D: Poor linearity

[Dimensional stability evaluation]

Line widths were measured using an optical microscope for the patterns in the 100 μm photomask portion of the substrate patterned at exposure doses of 30 mJ/cm 2 and 50 mJ/cm 2 . The increase in line width at an exposure dose of 50 mJ/cm 2 was calculated relative to the line width at an exposure dose of 30 mJ/cm 2 . The smaller the increase, the better the dimensional stability, and when the increase was less than 3 µm, it was evaluated as a usable level. That is, C and D are levels that are difficult to use.

S: Increment less than 1μm

A: The increment is 1 μm or more and less than 2 μm

B: The increment is 2 μm or more and less than 3 μm

C: increment of 3 μm or more and less than 5 μm

D: increment of 5 μm or more

[Development stability evaluation]

At the time of spray development, the pattern film thickness of filter segments formed by developing twice the appropriate time was compared based on the pattern film thickness formed by development for an appropriate development time. The rank of evaluation was as follows, and the usable level was set as the film thickness difference of less than 25%.

◎: Less than 15% difference in film thickness

○: More than 15% of film thickness difference and less than 25%

△: Over 25% and within 40% of film thickness difference

x: The film thickness difference exceeds 40%. Alternatively, defects or peeling have occurred.

As shown in Table 11, the filter segments formed using the photosensitive coloring compositions of Examples 101 to 121, 201 to 209, and 301 to 306 using the resin type dispersant (B) of the present application are Comparative Examples 101 to 104, 201 to Compared to the filter segments formed using 206 and 301 to 304, resolution, development stability, linearity and dimensional stability were good, and the pattern shape showed better characteristics.

In addition, when the ratio of one or more types of ethylenically unsaturated monomers selected from ethylenically unsaturated monomers (c) having a hydroxyl group is 35% to 100%, more preferably 38% to 60%, a more excellent pattern shape can be formed. Turns out. In addition, the photosensitive coloring composition prepared using the resin type dispersant B-22 had a high viscosity and was difficult to use. In addition, although the resin type dispersants B-14, B-15, B-16, and B-22 had good initial viscosities and were practically usable, thickening over time was recognized.

In addition, the double bond equivalent Z of the side chain of the resin type dispersant (B) calculated as ((c) weight + (d) weight) / ((meth) acryloyl group mol number in (d)) is 300 to 600 g / mol Phosphor resins (B-1) to (B-7) and (B-10) to (B-19) exhibited excellent characteristics in good pattern shapes compared to those without. In addition, when the content of the carboxy group-containing ethylenically unsaturated monomer in the ethylenically unsaturated monomer (c) was 2.5 to 10.0% by mass, more preferably 2.5% to 5%, excellent resolution was exhibited. It was also found that the photosensitive coloring composition in which the photopolymerization initiator (C) is C2 exhibits excellent dimensional stability in combination with the resinous dispersant (B) described in the present patent.

In addition, in RR-20, which is a comparative example having a high colorant content of 40% or more, compared to RR-25, which has a low colorant content, the patterning characteristics are worse, making it more difficult to use. However, as confirmed by RR-3 etc., according to the present invention, the photosensitive coloring composition having a high colorant content of 40% or more has equally good patterning properties compared to the photosensitive coloring composition RR-24 having a low colorant content. it turned out

<Production of color filters>

A black matrix was patterned on a glass substrate, and the red photosensitive coloring composition (RR-3) of the present invention was applied by a spin coater on the substrate so that x = 0.655 and y = 0.325 with a C light source to form a colored film. The film was irradiated with ultraviolet rays of 50 mJ/cm 2 through a photomask using an ultra-high pressure mercury lamp.

Then, spray development was performed with an alkaline developer composed of a 0.2% by mass sodium carbonate aqueous solution to remove the unexposed portion, followed by washing with ion-exchanged water, and heating the substrate at 220° C. for 20 minutes to form a red filter segment. By the same method, x = 0.147, y using the blue photosensitive coloring composition (RB-1) of the present invention so that the green photosensitive coloring composition (RG-1) of the present invention becomes x = 0.327, y = 0.614 = 0.049, a green filter segment and a blue filter segment were formed to obtain a color filter.

By using the photosensitive coloring composition of the present invention, a high-quality color filter was able to be produced.

Claims (6)

A photosensitive coloring composition for color filters containing a colorant (A), a resinous dispersant (B), a photopolymerization initiator (C), an organic solvent (D) and a polymerizable compound (E), wherein the resinous dispersant (B) comprises a molecule Ethylenically unsaturated monomer (b) containing a hydroxyl group in the presence of a reaction product between the hydroxyl group of the compound (a) having two hydroxyl groups and one thiol group and an acid anhydride group of any one of pyromellitic anhydride and trimellitic acid anhydride It is a resin obtained by reacting a hydroxyl group of a hydroxyl group-containing polymer obtained by polymerizing an ethylenically unsaturated monomer (c) containing, and an isocyanate group of a compound (d) having one isocyanate group and one or more (meth)acryloyl groups, and containing a hydroxyl group. The content of the structural unit derived from the ethylenically unsaturated monomer (b) is 35% by mass or more and 80% by mass or less with respect to the total amount of the structural unit derived from the ethylenically unsaturated monomer (c), and the content of the colorant (A) is It is 40 mass % or more with respect to the total amount of non-volatile matter of the photosensitive coloring composition for color filters, and the photoinitiator (C) is what contains an oxime ester type compound, The photosensitive coloring composition for color filters. According to claim 1,
((c) total mass of structural units derived from ethylenically unsaturated monomers + (d) total mass of structural units derived from compounds having one isocyanate group and one or more (meth)acryloyl groups) / ((d ) The double bond in the side chain of the resin type dispersant (B) represented as the number of moles of (meth)acryloyl groups contained in the structural unit derived from the compound having one isocyanate group and one or more (meth)acryloyl groups The photosensitive coloring composition for color filters whose equivalent weight (Z) is 300-600 g/mol. According to claim 1 or 2,
The content of the structural unit derived from the hydroxyl group-containing ethylenically unsaturated monomer (b) in the resin type dispersant (B) is 38% by mass or more and 60% by mass or less with respect to the total amount of the structural unit derived from the ethylenically unsaturated monomer (c) , Photosensitive coloring composition for color filters. delete delete The color filter provided with the filter segment formed from the photosensitive coloring composition for color filters of Claim 1 or 2 on a base material.